Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin

ABSTRACT

A quaternized polymer for use as a cosmetic agent, has recurring units of the formula ##STR1## wherein R is lower alkyl or --CH 2  --CH 2  OH; 
     R&#39; is an aliphatic, alicyclic or arylaliphatic radical containing a maximum of 20 carbon atoms, or R and R&#39; together with the nitrogen atom to which they are attached form a heterocycle capable of containing a heteroatom other than nitrogen; 
     A is a divalent group selected from 
     (1) o-, m- or p-xylylidene of the formula ##STR2## (2) ##STR3##  wherein x, y and t are whole numbers ranging from 0 to 11 such that the sum (x+y+t) is greater than or equal to 0 and lower than 18, and E and K represent hydrogen or an aliphatic radical having less than 18 carbon atoms, 
     (3) --(CH 2 ) n  --S--(CH 2 ) n  --, 
     (4) --(CH 2 ) n  --O--(CH 2 ) n  --, 
     (5) --(CH 2 ) n  --S--S--(CH 2 ) n  --, 
     (6) --(CH 2 ) n  --SO--(CH 2 ) n  --, 
     (7) --(CH 2 ) n  --SO 2  --(CH 2 ) n  -- and 
     (8) ##STR4##  wherein n is equal to 2 or 3; B represents a divalent group selected from 
     (1) o-, m- or p-xylylidene of the formula ##STR5## (2) ##STR6##  wherein D and G represent hydrogen or an aliphatic radical having less than 18 carbon atoms and v, z, and u are whole numbers ranging from 0 to 11, with two of v, z and u simultaneously being capable of being 0, such that the sum (v+z+u) is greater than or equal to 1 and lower than 18 and such that the sum (v+z+u) is greater than 1 when the sum (x+y+t) is equal to 0, 
     (3) ##STR7##  and (4) --(CH 2 ) n  --O--(CH 2 ) n  -- 
      wherein n is 2 or 3; and 
     X⊖ is an anion derived from an organic or mineral acid. The quaternized polymer is employed in cosmetic compositions for the hair and skin.

This application is a divisional of Ser. No. 163,411, filed Jun. 26,1980, now U.S. Pat. No. 4,422,853, which is a continuation-in-part ofSer. No. 849,657, filed Nov. 8, 1977, now U.S. Pat. No. 4,217,914, whichis a continuation of Ser. No. 577,836, filed May 15, 1975, nowabandoned.

The present invention relates to the use, in a cosmetic composition, ofpolymers possessing quaternized ammonium groups, to cosmeticcompositions containing these polymers, and to a process for treatinghair or the skin with said compositions.

The polymers of the present invention are, more particularly, cationicpolymers having quaternized nitrogen atoms which are part of themacrochain.

Certain polymers of this type are known and have already been proposedfor use as pesticidal agents, flocculation agents, surfactants or as ionexchange agents.

It has now surprisingly been discovered that such polymers exhibitinteresting cosmetic characteristics when they are incorporated intocompositions which are applied to the hair or skin.

One embodiment of the present invention relates to the use as a cosmeticagent, and principally to the use in the preparation of cosmeticcompositions, of quaternized polymers having recurrings units of formulaI ##STR8## wherein X.sup.⊖ represents an anion derived from a mineral ororganic acid;

R is lower alkyl or --CH₂ --CH₂ --OH;

R' is an aliphatic, alicyclic or an arylaliphatic radical, containing amaximum of 20 carbon atoms; R and R' together with the nitrogen atom towhich they are attached can form a ring capable of containing a secondheteroatom other than nitrogen;

A represents a divalent group of the formula ##STR9## wherein x, y and tare whole numbers ranging from 0 to 11 and such that the sum (x+y+t) isgreater than or equal to 0 and lower than 18, and E and K representhydrogen or an aliphatic radical having less than 18 carbon atoms. A canalso represent a divalent group of the formula: ##STR10## wherein n is awhole number equal to 2 or 3; and B represents a divalent group of theformula ##STR11## wherein n has the meaning given above.

As indicated above, certain polymers of formula I are known while othersare new.

In that which follows and for the sake of simplicity, polymers whoserecurring units correspond to formula I will be designated by theexpression "polymers of formula I".

The terminal groups of polymers of formula I can vary with the amount ofinitial reactants employed to produce the same. They can be either ofthe type ##STR12## or of the type X--B--.

In formula I, X⁻ represents principally a halide anion such as bromide,iodide or chloride, or an anion derived from other mineral acids, suchas phosphoric acid, sulfuric acid and the like, or even an anion derivedfrom an organic sulfonic or carboxylic acid, principally an alkanoicacid having 2-12 carbon atoms, for example, acetic acid, aphenylalkanoic acid, for example, phenylacetic acid, benzoic acid,lactic acid, citric acid or paratoluene sulfonic acid. The substituent Rrepresents, preferably, an alkyl group having from 1 to 6 carbon atoms.When R' represents an aliphatic radical, the same generally is alkyl orcycloalkyl wherein the alkyl has less than 20 carbon atoms andpreferably not more than 16 carbon atoms. When R' represents analicyclic radical, the same generally is cycloalkyl having 5 or 6chains. When R' represents an arylaliphatic radical, the same generallyis aralkyl such as phenylalkyl wherein the alkyl moiety has, preferably,1-3 carbon atoms. When both R and R' and the nitrogen atom to which theyare attached form a ring, R and R' can represent together, principally,a polymethylene radical having 2 to 6 carbon atoms, and the ring caninclude a second heteroatom, such as oxygen or sulfur. When thesubstituents E, K, D or G are an aliphatic radical, they generally arean alkyl having from 1 to 17 carbon atoms and preferably 1 to 12 carbonatoms; v, z and u represent, preferably, numbers ranging from 1 to 5.Two of them, of course, can be equal to zero; x, y and t are preferablynumbers ranging from 0 to 5. When A or B represents a xylylidene radicalit can be an o-, m- or p-xylylidene group.

Among the polymers of formula I, those compounds which preferably areemployed for cosmetic use according to the present invention are,notably, those for which R is methyl or hydroxyethyl; R' is alkyl having1-16 carbon atoms or benzyl or cyclohexyl; or R and R' representtogether --(CH₂)₅ -- or --(CH₂)₂ --O--(CH₂)₂ --; A is xylylidene or apolymethylene having 2-12 carbon atoms, optionally branched by one ortwo alkyl substituents having 1-12 carbon atoms, or ##STR13## or apolymethylene having 4 or 6 carbon atoms and including a heteroatomgroup of the type --O--, --S--, --S--S--, --SO-- or --SO₂ --; B is axylylidene radical or a polymethylene having 3 to 10 carbon atomsoptionally branched by one or two alkyl substituents having 1-12 carbonatoms or ##STR14## or a polymethylene radical having 4 or 6 carbon atomsand carrying an oxygen heteroatom; and X is chlorine or iodine orbromine.

It is to be understood that the invention also relates to the cosmeticuse of polymers of formula I wherein A, B, R or R' have severaldifferent values in the same polymer I.

The preparation of such polymers is given in the following descriptionand Example 43 is an illustration of the same.

The polymers of formula I can be prepared principally in accordance withthe following procedures.

PROCESS 1

This process comprises polycondensing a di-tertiary diamine of theformula ##STR15## and a dihalide of the formula X--B₁ --X, R, R' and Xhave the meanings given above; A₁ represents A when B₁ represents B, andA₁ represents B when B₁ represents A, A and B being defined above.

This process for preparing polymers of formula I can be effected inaccordance with one of the two following methods: ##STR16##

When A has one of the following values: ##STR17## Process 1a ispreferably employed.

For example, the polycondensation reaction is carried out in a solventor in a mixture of solvents which favor a quaternization reaction. Suchsolvent(s) include water, dimethyl formamide, acetonitrile, loweralcohols, principally lower alkanols such as methanol, and the like.

The reaction temperature can range between 10° and 150° C., preferablybetween 20° and 100° C.

The reaction time can depend on such easily determined factors as thenature of the solvent employed, the initial reactants used as well asthe degree of polymerization desired.

Generally, the initial reactants are employed in equimolar quantities,but it is possible to employ either the diamine or the dihalide inslight excess, this excess being lower than 20 mole percent.

The resulting polycondensate is isolated at the end of the reactioneither by filtration or by concentrating the reaction mixture.

It is possible to regulate the average length and the polymer chain byadding, at the beginning, or during the course of the reaction, a smallquantity, for instance, 1-15 mole percent relative to one of the initialreactants, of a monofunctional reactant such as a tertiary amine or amonohalide. In this case a portion, at least, of the terminal groups ofthe polymer I produced is constituted either by the tertiary amine groupused, or by the hydrocarbon group of the monohalide employed. Someillustrations of limiting the length of the chain by the addition ofvariable quantities of triethylamine are given in Examples 47 to 49,below.

The present invention also relates to the cosmetic use of the polymersof formula I having such terminal groups.

There can also be employed as the initial reactants a mixture ofdi-tertiary diamines, or a mixture of dihalides, or even a mixture ofdi-tertiary amines and a mixture of dihalides with the proviso that theratio of the total molar quantities of diamines and dihalides is near l,as illustrated, for instance, in Example 43.

PROCESS 2

This process comprises self-polycondensing a tertiary ω-halogenatedamine of the formula ##STR18##

In this case, the polymer obtained corresponds to general formula Iwherein B=A, and R, R' and X have the meanings given above except that Acan only be ##STR19## the sum (x+y+t) necessarily being in this casegreater than 4.

This reaction can be conducted either in the absence of a solvent orwith the same solvents as in Process 1 and by using the same reactiontemperature ranges indicated therefor. As before, a monofunctionalreactant can be added to the reaction medium to regulate the degree ofpolycondensation. Further, a mixture of several tertiary ω-halogenatedamines can also be employed.

In the two processes for preparing the polymers of formula I mentionedabove, the resulting polycondensate is isolated at the end of thereaction either by filtration, or by concentration of the reactionmixture and optional crystallization by the addition of an appropriateanhydrous organic liquid, for example, acetone.

The di-tertiary diamines used as initial reactants in Process 1, above,can be prepared in accordance with one of the methods given below.

METHOD 1

A primary amine of the formula R--NH₂ is reacted with a dihalide of theformula Hal--A₁ --Hal, Hal being a halogen atom and preferably an atomof bromine or iodine. The reaction is carried out at a temperaturebetween about 50° and 150° C. and an excess of primary amine isemployed, i.e. generally 2 to 5 moles of primary amine per mole ofdihalide are used. After treatment of the reaction mixture with a basicsolution, for example, a solution of NaOH or KOH, a di-secondary diamineof the formula R--NH--A₁ --NH--R is obtained. This latter product isthen submitted to an alkylation reaction in accordance with conventionalprocedures, the expression "alkylation" meaning here the substitution ofa hydrogen atom linked to the nitrogen by a R' group such as definedabove. Then, in accordance with usual procedures, the di-tertiarydiamine of the formula ##STR20## is separated from the reaction mixture.

METHOD 2 Applicable in the case wherein A₁ is a xylylidene or alkyleneradical

A primary amine of the formula R--NH₂ is reacted with an arylsulfonylhalide of the formula Ar--SO₂ --Hal, Ar being an aryl group, forexample, phenyl or tolyl, and Hal being a halogen, such as a chlorineatom. A sulfonamide of the formula Ar--SO₂ --NHR is obtained which isthen submitted to an alkylation reaction in accordance with knownprocedures to form a sulfonamide of the formula ##STR21## which, by acidhydrolysis employing for instance an aqueous sulfuric acid solution,procedures a secondary amine of the formula ##STR22## This latterproduct is then reacted with a dihalide of the formula Hal--A₁ --Hal,Hal and A being defined above in the presence of a tertiary amine suchas N-ethyl diisopropylamine, by using at least two moles of secondaryamine and tertiary amine per mole of dihalide. The reaction is carriedout, preferably, in the absence of a solvent and at a temperaturebetween 50° and 130° C. At the end of the reaction, the mixture is takenup in water to dissolve the amine salts formed, and the mixture isextracted with an appropriate solvent such as, for example, ethylacetate. The resultant extract is then initially washed with an aqueousalkaline solution (NaOH or KOH) and then with water. The organic phaseis then dried and the di-tertiary diamine is isolated either bydistillation, or by concentration under reduced pressure.

METHOD 3

A primary amine of the formula RNH₂ is reacted with an arylsulfonylhalide, as indicated in Method 2. The resulting sulfonamide of theformula Ar--SO₂ --NHR is then reacted with a dihalide of the formulaHal--A₁ --Hal, at a temperature between about 80° and 140° C. Theresulting disulfonamide, of the formula ##STR23## can be directlysubmitted, without being isolated, to acid hydrolysis. This acidhydrolysis can, for example, be carried out in an 85% aqueous solutionof sulfuric acid, at a temperature between about 120° and 145° C., for aperiod of about 7 to 20 hours. The resulting di-secondary diamine, ofthe formula ##STR24## is then submitted to an alkylation reaction, inaccordance with known procedures to form a di-tertiary diamine of theformula ##STR25##

Method 3 is particularly useful in the case where A₁ =(CH₂)₅, for itavoids parasitic cyclization reaction observed with Methods 1 and 2 inthis case.

METHOD 4

A secondary amine of the formula ##STR26## is reacted with a dihalide ofthe formula Hal--A₁ --Hal, Hal and A₁ having the meanings given above,in the presence of an alkaline carbonate or a tertiary amine such asN-ethyl diisopropylamine.

When the reaction is carried out in the presence of an alkalinecarbonate at least one mole of carbonate per mole of dihalide isemployed. Ethanol is generally used as the solvent. At the end of thereaction, the mineral salts formed are filtered; the ethanol is expelledunder reduced pressure; and the reaction products are separated bydistillation.

When the reaction is carried out in the presence of a tertiary amine, atleast two moles of secondary amine and tertiary amine per mole ofdihalide are employed. The reaction is carried out, preferably, in theabsence of a solvent and at a temperature between 50° and 130° C. At theend of the reaction, the mixture is taken up in water to dissolve theamine salts formed and the resulting mixture is extracted with anappropriate solvent such as, for example, ethyl acetate. The extract iswashed initially with an aqueous alkaline solution, NaOH or KOH, andthen with water. The organic phase is then dried and the di-tertiarydiamine is isolated either by distillation, or by concentration underreduced pressure.

The secondary amine initial reactants wherein R'=--CH₂ --CH₂ --OH, areprepared by reacting a halogenated derivative of the formula R-Hal withmonoethanol amine.

The secondary amine initial reactants, wherein R is other than --CH₂--CH₂ OH, are obtained, for example, by reacting a primary amine of theformula R--NH₂ with an arylsulfonyl halide of the formula Ar--SO₂ --Hal,Ar being an aryl group, for example phenyl or tolyl, and Hal being ahalogen atom, for example a chlorine atom. A sulfonamide of the formulaAr--SO₂ --NHR is thus obtained which is then submitted to an alkylationreaction in accordance with known methods to form a sulfonamide of theformula ##STR27## which, by acid hydrolysis, which includes the use ofan aqueous solution of sulfuric acid, leads to a secondary amine of theformula ##STR28##

METHOD 5 Applicable in the case where A₁ represents --CH₂ --CHOH--CH₂ --

Epichlorohydrin is reacted with a secondary amine of the formulaR--NH--R', employed preferably in excess. The reaction is carried out insolution or in suspension, in water, at a temperature between 40° and100° C., with 3 to 10 moles of secondary amine per mole ofepichlorohydrin being employed. After treatment of the reaction mixturewith a basic solution, for example, a solution of NaOH or KOH, andextraction with an appropriate solvent, for example, ethyl acetate, amixture of initial secondary amine and di-tertiary diamine is recoveredand then separated by distillation.

METHOD 6 Applicable in the case where A₁ represents --(CH₂)_(n)--S--S--(CH₂)_(n) --

An alkaline thiosulfate is reacted with an amine of the formula##STR29## to form a Bunte salt that is hydrolyzed into the disulfide bymeans of an alkaline solution of NaOH or KOH. The reaction is carriedout in water at a temperature between 40° and 100° C. As soon as theBunte salt is completely formed, the corresponding disulfide ishydrolyzed and extracted in an appropriate solvent such as ethylacetate. One eliminates the solvent by distillation under reducedpressure and isolates the di-tertiary diamine which can be purified, ifdesired, by distillation under reduced pressure.

The tertiary ω-halogenated amine used as an initial reactant in Process2 described above can be prepared by utilizing the processes, describedby M. R. Lehman, C. D. Thompson and C. S. Marvel, J.A.C.S. 55, 1977(1933) and by Littman and Marvel, J.A.C.S. 52, 287, (1930), by replacingthe dimethylamine initial reactant with an appropriate secondary amineof the formula ##STR30## with R and R' being defined above. They canalso be obtained by the reaction, in the presence of a proton acceptor,such as N-ethyl diisopropylamine, of a compound of the formulaBr--A--OC₆ H₅ with a secondary amine of the formula ##STR31## wherein A,R and R' have the meanings given above, followed by treatment of theresulting compound of the formula ##STR32## with H Br under theconditions described in the two J.A.C.S. references noted above.

Although the invention is not limited to the use of polymers I with anyspecified degree of polymerization, it will be noted that the polymersof formula I preferably employed in the present invention have amolecular weight ranging generally between 5,000 and 50,000. Thesepolymers are generally soluble in at least one of the following threesolvents: water, ethanol or a water-ethanol mixture. By evaporation ofsuch a solvent from a solution of the polymer it is possible to obtainfilms which exhibit a good affinity for hair.

As indicated above, the polymers of formula I exhibit interestingcosmetic characteristics which permit their use in the preparation ofcosmetic compositions.

Thus, the present invention also relates to a cosmetic compositioncharacterized by the fact that it includes at least one polymer offormula I. Such cosmetic compositions include generally at least oneadjuvant conventionally employed in cosmetic compositions.

The cosmetic compositions of the present invention include the polymersof formula I either as the principal active component or as an additive.

These cosmetic compositions can be provided in the form of aqueous,alcoholic or hydroalcoholic solutions, the alcohol being principally alower alkanol such as ethanol or isopropanol, or in the form of a cream,gel, emulsion, or even in the form of an aerosol packaged under pressurein an aerosol container together with an aerosol propellant.

The adjuvants generally provided in the cosmetic compositions of thepresent invention are, for example, perfumes, dyes, preservatives,sequesterants, thickening agents and the like.

It is pointed out that the cosmetic compositions of the presentinvention can be ready-to-use compositions as well as concentratedcompositions that are diluted before use. Thus, the cosmeticcompositions of the invention are then not limited to any particularmaximum concentration of the polymer of formula I contained therein.

In the cosmetic compositions of the present invention, the concentrationof the polymers of formula I is at least 0.25% by weight. Generally,said concentration is between 0.5 and 10, preferably between 0.5 and 5,percent by weight.

The polymers of formula I exhibit principally interesting cosmeticproperties when they are applied to the hair.

Thus, the present invention also relates to a process for treating hairwhich comprises applying to the hair the cosmetic composition definedabove and containing at least one polymer of formula I, said compositionbeing applied in an amount sufficient to provide a protective effect forthe hair and/or to improve the quality of the hair.

When such a composition is applied to the hair, which composition canalso contain other active substances for use in such treatments as ashampooing, dyeing, hair setting or the like, the compositionsignificantly improves the quality of the hair and/or provides aprotective effect for the hair.

For example, the composition of this invention provides protection tothe hair by assisting and facilitating the untangling of wet or dryhair. Further, even when present in high concentrations in the cosmeticcomposition, the polymers of formula I do not impart a sticky feeling tothe hair, wet or dry.

Moreover, unlike conventional cationic agents, the polymers of formula Ido not render dry hair heavy. Thus, they facilitate the creation ofbouffant hair styles and impart to dry hair such qualities as livelinessand a shiny appearance.

Moreover, polymers of formula I contribute effectively to theelimination of the drawbacks of hair sensitized by such treatments asbleaching, permanent waving or dyeing. It is known, for instance, thatsensitized hair is often dry, dull and rough, and difficult to untangleand style and the use of polymers of formula I in compositions forsensitized hair overcomes such drawbacks.

Thus said polymers have a protective effect on hair, particularly ondegraded hair.

Further, polymers of formula I exhibit, in particular, a great interestwhen they are employed as pretreating agents, principally before ananionic and/or nonionic shampoo, or before an oxidation dyeing, itselffollowed by an anionic and/or nonionic shampoo. The hair is thenparticularly easy to untangle and has a very soft feel.

Thus said polymers have also a protective effect on hair when appliedbefore a cosmetic treatment, particularly before treatments having adegrading effect on hair.

These polymers are also useful as pretreating agents for other hairtreatment operations, such as a permanent waving operation.

The cosmetic compositions according to the invention are principallycosmetic compositions for the hair, characterized by the fact that theyinclude at least one polymer of formula I.

These cosmetic compositions for the hair include, generally, at leastone adjuvant conventionally employed in cosmetic compositions for thehair.

These cosmetic compositions for the hair can be provided in the form ofan aqueous, alcoholic or hydroalcoholic solution, the alcohol being alower alkanol such as ethanol or isopropanol, or in the form of a cream,gel, emulsion or even in the form of a spray. They can also be packagedin the form of an aerosol under pressure in an aerosol containertogether with an aerosol propellant such as nitrogen, nitrous oxide or aFreon-type chlorofluorinated hydrocarbon.

The adjuvants generally provided in the cosmetic compositions for thehair in accordance with the present invention are for example, perfumes,dyes, preservatives, sequesterants, thickening agents, emulsifiers andthe like, or even cosmetic resins conventionally employed in cosmeticcompositions for the hair.

The polymers of formula I can be provided, in accordance with thepresent invention, either as an additive or as the principal activecomponent in such cosmetic compositions as hair setting lotions, hairtreating lotions, styling creams or gels. They can also be employed asan additive in shampoo compositions, hair setting compositions, hairrestructuring lotion compositions, hair dye compositions, permanentwaving compositions, anti-dandruff treating lotion compositions or hairlacquer compositions.

The cosmetic compositions for the hair according to the inventioninclude then principally:

(a) hair treating compositions characterized in that they include, asthe active components, at least one polymer of formula I in an aqueousor hydroalcoholic solution. The amount of polymer of formula I in suchcompositions can range between 0.25 and 10 percent by weight and,preferably, between 0.5 and 5 percent by weight of said composition.

The pH of these treating compositions is close to neutral and can range,for example, from 6 to 8. If necessary, the pH of such compositions canbe adjusted to the value desired, by adding either an acid, such ascitric acid, or a base, principally an alkanolamine such asmonoethanolamine or triethanolamine.

To treat the hair with such a composition, the said composition isapplied to wet hair and is permitted to remain in contact therewith forabout 3 to 15 minutes. Thereafter, the hair is rinsed. If desired, thethus treated hair can then be subjected to a conventional hair settingoperation;

(b) shampoo compositions characterized by the fact that they include atleast one polymer of formula I and a cationic, nonionic or anionicdetergent.

Representative cationic detergents usefully employed include,principally, long chain quaternary ammoniums, esters of fatty acids andamino alcohols or polyether amines.

Representative nonionic detergents are principally esters of polyols andsugars, polyethers of polyhydrogenated fatty alcohol and condensationproducts of ehtylene oxide on fatty bodies or on long chain alkylphenols or on long chain mercaptans or on long chain amides.

Representative anionic detergents are, principally, the alkaline salts,the ammonium salts or the amine or amino alcohol salts of fatty acids,such as oleic acid, ricinoleic acid, copra oil acids or hydrogenatedcopra oil acids; the alkaline salts, the ammonium salts or the aminoalcohol salts of the sulfates of fatty alcohols, principally fatty C₁₂-C₁₄ and C₁₆ alcohols; the alkaline salts, the magnesium salts, theammonium salts or the amino alcohol salts of the suflates ofoxyethylenated fatty alcohols; the condensation products of fatty acidswith isethionates, or with taurine, or with methyltaurine or withsarcosine and the like; alkylbenzene sulfonates, principally thosewherein the alkyl moiety has 12 carbon atoms; alkylarylpolyethersulfates; monoglyceride sulfates and the like. All these anionicdetergents, as well as numerous others not cited here, but which can beemployed in the present invention, are well known and described in theliterature.

These shampoo compositions can also contain various ajuvants such as,for example, perfumes, dyes, preservatives, thickening agents, foamstabilizers, softening agents or even one or more cosmetic resins.

In these shampoo compositions, the concentration of the detergentgenerally ranges between 5 and 50 weight percent and the concentrationof the polymer of formula I generally ranges between 0.5 and 10 weightpercent and preferably between 0.5 and 5 weight percent;

(c) hair setting lotions, principally, for sensitized hair,characterized by the fact that they contain at least one polymer offormula I, in an aqueous, alcoholic or hydroalcoholic solution.

Such hair setting lotions can also contain another cosmetic resin. Thecosmetic resins useful in such lotions can be quite varied. They areprincipally vinylic or crotonic homopolymers or copolymers as, forexample, polyvinyl pyrrolidone, copolymers of vinyl pyrrolidone andvinyl acetate, copolymers of crotonic acid and vinyl acetate and thelike.

The concentration of the polymer of formula I in these hair settinglotion compositions can range generally between 0.25 and 10 weightpercent and preferably between 0.5 and 3 weight percent. The othercosmetic resin can be present in essentially the same proportions.

The pH of these hair setting lotion compositions ranges generallybetween 3 and 9 and preferably between 4.5 and 7.5. The pH can beadjusted, if desired, by the addition, for example, of an alkanolaminesuch as monoethanolamine or triethanolamine;

(d) hair dye compositions characterized by the fact that they include atleast one polymer of formula I, a dye and a carrier. Preferably, thecarrier is selected so that the composition is a cream.

The concentration of the polymers of formula I in such hair dyecompositions can range between 0.5-10 weight percent and preferablybetween 0.5 and 5 weight percent.

When the dye composition contains an oxidation dye, the dye compositioncan be packaged in two parts, one part containing both the oxidation dyeand the polymer of formula I and the other part containing the oxidizingagent such as hydrogen peroxide. The two parts are mixed at the momentof use;

(e) hair lacquer compositions characterized by the fact that theyinclude an alcoholic or hydroalcoholic solution of a conventional hairlacquer cosmetic resin and at least one polymer of formula I, thiscomposition being packaged in an aerosol container, under presssure,together with an aerosol propellant.

A typical aerosol hair lacquer composition in accordance wtih thepresent invention can be provided by adding a conventional cosmeticresin and the polymer of formula I to a mixture of an anhydrousaliphatic alcohol, such as ethanol or isopropanol, and a propellant or amixture of liquified propellants such as halogenated hydrocarbonsincluding trichlorofluoromethane, dichloro difluoromethane and mixturesthereof.

In these hair lacquer compositions, the concentration of the cosmeticresin ranges generally between 0.5 and 3 weight percent, and theconcentration of the polymer of formula I ranges generally between 0.25and 10 weight percent.

However, it is possible to add to these hair lacquer compositions, inaccordance with the invention, such adjuvants as dyes, plasticizers orany other conventional adjuvant;

(f) hair restructuring lotion compositions characterized by the factthat they include at least one agent having hair restructuringcharacteristics and at least one polymer of formula I.

The restructuring agents usefully employed in such lotions are, forexample, methylol derivatives described in French Pat. Nos. 1,519,979;1,159,980; 1,519,981; 1,519,982 and 1,527,085.

In these hair structuring lotions the concentration of the restructuringagent ranges generally between 0.1 and 10 weight percent and theconcentration of the polymer of formula I ranges generally between 0.25and 10 weight percent; and

(g) pre-treatment compositions provided principally in the form ofaqueous or hydroalcoholic solutions, optionally packaged in aerosolcontainers, or in the form of a cream or gel and capable of beingapplied to the hair before shampooing, principally before an anionicand/or nonionic shampooing and before oxidation dyeing followed byanionic and/or nonionic shampooing, or even before a permanent wavetreatment.

In these pre-treatment compositions, the polymer of formula Iconstitutes the principal active component, and its concentration variesgenerally from 0.25 to 10 weight percent and preferably from 0.5 to 5weight percent thereof. The pH of these compositions, approachingneutral, ranges generally between 3 and 9 and principally between 6 and8.

These pre-treatment compositions can contain various adjuvants, forexample, cosmetic resins conventionally employed in cosmeticcompositions for the hair. They can also include pH modifiers, forexample, amino alcohols such as monoethanolamine and triethanolamine.

The polymers of formula I also exhibit interesting cosmetic propertieswhen they are applied to the skin.

Principally, they assist in the hydration of the skin and avoid then itsdrying out. They also impart to the skin a significant soft feeling.

The cosmetic compositions according to the invention can be cosmeticcompositions for the skin characterized by the fact that they include atleast one polymer of formula I.

Moreover, these compsoitions can include generally at least one adjuvantconventionally employed in cosmetic compositions for the skin and can beprovided in the form of creams, gels, emulsions or aqueous, alcoholic orhydroalcoholic solution.

The concentration of the polymer of formula I in these compositions forthe skin ranges generally between 0.25 or 0.5 and 10 weight percent.

The adjuvants generally employed in these cosmetic compositions are, forexample, perfumes, dyes, preservatives, thickening agents,sequesterants, emulsifiers and the like.

These compositions for the skin constitute principally treating creamsor lotions for the hands or face, anti-solar creams, tining creams,make-up remover milks, bubble bath formulations or even deodorantcompositions and can be prepared in accordance with conventionalprocedures.

For example, to obtain a cream, an aqueous phase containing in solutionthe polymer of formula I and optionally other components can beemulsified with an oil phase.

The oil phase can be made up of various materials such as paraffin oil,vaseline oil, sweet almond oil, avacado oil, olive oil, esters of fattyacids such as glyceryl monostearate, ethyl or isopropyl palmitate andalkyl myristates, such as the myristates of propyl, butyl or cetyl.Further, fatty alcohols such as cetyl alcohol or waxes such as, forexample, beeswax can be added to such compositions.

The polymers of formula I can be provided, in accordance with thepresent invention, either as an additive, or as the principal activecomponent, in such cosmetic compositions for the skin or treating creamsor lotions for the hands or face, or as an additive in such compositionsas anti-solar creams, tinting creams, make-up remover milks, bath oilformulations or bubble bath formulations and the like.

More particularly, the present invention relates to cosmeticcompositions as defined above which include at least one of any one ofthe polymers described hereafter in Example 1-140. These particularcosmetic compositions are either those for the hair or for the skin.

The present invention also relates to a process as defined above for acosmetic treatment characterized by the fact that there is applied tothe hair or to the skin at least one polymer of formula I in a cosmeticcomposition based on the polymer of formula I as defined above.

In particular, the present invention relates to a process for treatinghair comprising applying to the hair, before an anionic shampoo orbefore an oxidation dyeing followed by an anionic shampooing, apre-treatment composition containing at least one polymer of formula Ias defined above.

The following non-limiting examples illustrate the present invention.

EXAMPLES OF PREPARING INITIAL REACTANT DIAMINES PREPARATION NO. 1N,N'-dibutyl-N,N'-dimethyl diamino 1,6-hexane

(a) 61 g of 1-dibromo hexane are slowly added, with agitation, to 91 gof n-butylamine previously heated to 75° C. At the end of the addition,the hydrobromide formed crystallizes and the tmperature rises to 110° C.The reaction mixture is then cooled to 60° C. and there are introduced,successively, 250 cc of water and 50 cc of a concentrated aqueoussolution of NaOH.

The agitation of the reaction mixture is continued for 1/2 hour.Thereafter, the precipitate, which is 1,6-N-N'-dibutyl dimaino hexane,is separated from the reaction mixture by filtration and dried.

(b) 37 g of this latter product are added, with agitation and whilemaintaining the temperature lower than +5° C., to a mixture of 108 g ofpure formic acid and 11 g of water. There are then introduced over a 10minute period, 117 g of a 30% aqueous solution of formaldehyde. Thetemperature is then brought slowly to 100° C. The resulting mixture isagitated at this temperature until the end of the evolution of CO₂. Thereaction mixture is then concentrated under reduced pressure and theresidue made alkaline by the addition of about 150 cc of a concentratedaqueous solution NaOH. This mixture is then extracted three times with200 cc of isopropyl ether. The combined organic phases are worked threetimes with 100 cc of water, dried and concentrated. The residue is thendistilled under vacuum and 72 g of 1,6-N,N'-dibutyl-N,N'-dimethyldiamino hexane, distilling at 98°-99° C., under 0.1 mm Hg are recovered.

PREPARATION NO. 2 1,3-N,N'-dimethyl-N,N'-dioctyl diamino propane

(a) N-methyl octylamine

523 g of benzene sulfonamide of octylamine are dissolved in 1500 cc ofanhydrous xylene. There are then introduced, with agitation, 835 cc of a2.4N ethanolic solution of sodium ethylate. The ethanol is theneliminated by distillation. While agitating the reaction mixture andmaintaining its temperature at 100°-110° C., there are introduced over aone hour period 385 cc of methyl sulfate. The resulting mixture isheated at reflux for 4 hours. After cooling, the mineral salts formedare removed by filtration. There are then added to the filtrate 1500 ccof a concentrated aqueous solution of NaOH. The resulting mixture isdecanted and the xylenic phase is washed 4 times with 1000 cc of waterand then concentrated. The residue obtained is added to a mixture of1400 g of concentrated sulfuric acid and about 560 g of crushed ice. Theresulting mixture is then brought, with agitation, to 160° C. for 16hours. After cooling, the reaction mixture is poured onto 3 kg ofcrushed ice and made alkaline by the addition of 3500 cc of aconcentrated aqueous solution of NaOH, which is then extracted threetimes with 2000 cc of ethyl acetate. The organic phase is then washedwith water, dried and concentrated under reduced pressure. The residueis distilled and the fraction distilling at 45°-50° C. under 0.2 mm Hgis recovered.

(b) 1,3-N,N'-dimethyl-N,N'-dioctyl diamino propane

69 g of 1,3-dibromo propane are added to a mixture of 107 g of N-methyloctylamine and 87.5 g of N-ethyldiisopropyl amine while maintaining thetemperature at 100°-150° C. The resulting mixture is agitated for 7hours at 120° C., and then cooled. To the cooled mixture there are added500 cc of water and 200 cc of ether. The aqueous phase is decanted andthe ether phase, treated with 50 cc of a concentrated aqueous solutionof NaOH, is then decanted and washed three times with 100 cc of water.After drying, the ether is evaporated and then the unreacted N-methyloctylamine reactant is evaporated. The residue obtained includes twophases which are separated.

The upper clear phase is purified by distillation and the1,3-N-N'-dimethyl-N,N'-dioctyl diamino propane distilling at 150°-153°C. under 0.5 mm Hg is recovered.

PREPARATION NO. 3 1,5-N,N'-didecyl-N,N'-dimethyl diamino pentane

(a) 1,5-N,N'-didecyl diamino pentane

297 g of the benzene sulfonamide of N-decylamine are reacted with sodiumethylate, in a manner analogous to that described in Preparation No. 2,to form the corresponding sodium-containing derivative. After havingeliminated the ethanol by evaporation, there are introduced, withagitation and at a temperature near 120° C., 162 g of 1,5-diiodopentane.The resulting mixture is heated for 4 hours at reflux of the xylene andthen cooled. To the cooled mixture there are added with agitation, 500cc of water to dissolve the mineral salts formed.

The organic phase is then decanted, dried and concentrated under reducepressure. The residue obtained is heated for 14 hours at 130° C. in thepresence of 300 cc of 85% sulfuric acid. After cooling, the reactionmixture is poured onto 1.5 kg of crushed ice. The pH is brought to 10 bythe addition of a 30% aqueous solution of NaOH. The precipitate formedis separated by filtration, washed with water and dried.1,5-N,N'-didecyl diamino pentane is thus obtained.

(b) 1,5-N,N'-didecyl-N,N'-dimethyl diamino pentane

By methylating the product obtained in paragraph (a) above, inaccordance with a method analogous to that described in Preparation No.1, 1,5-N,N'-didecyl-N,N'-dimethyl pentane, B.P.=193°-195° C. (0.4 mmHg), is obtained.

PREPARATION NO. 4 1,3-N,N'-didodecyl-N,N'-dimethyl diamino propanol-2

26.6 g of epixhlorohydrin are slowly added to a vigorously agitatedmixture of 370 g of N-methyl dodecylamine and 600 cc of water. At theend of the addition, the reaction mixture is heated to 90° C. for 12hours. After cooling, 10 cc of a concentrated aqueous solution of NaOHare added and the resulting mixture is extracted three times with 200 ccof ethyl acetate. The extraction solutions are dried on sodium sulfateand concentrated under reduced pressure. A first fraction correspondingto the excess N-methyl dodecylamine is thus obtained. A second fraction,distilling at 235°-240° C. under 1.5 mm Hg which is the desireddi-tertiary diamine is recovered.

PREPARATION NO. 5 1,3N,N'-di(2-hydroxy)ethyl-N,N'-dioctyl diaminopropane

There is heated at reflux for 50 hours the following mixture:

100 g of N-(2-hydroxy)ethyl octylamine,

28.6 g of 1,3-dibromo propane,

22 g of potassium carbonate, and

300 cc of ethanol.

The mineral salts formed are removed by filtration; the ethanol isdistilled off under reduced pressure; and then the residue is distilledunder vacuum. The expected diamine distills at 200°-206° C. under 1 mmHg.

PREPARATION NO. 6

44 g of N-butyl-N-methyl 2-bromo ethylamine are dissolved in 10 cc ofwater. Then, while maintaining the temperature in the neighborhood of 0°C., the pH of the solution is adjusted to 7 by the addition of diluteNaOH. Then the temperature of the solution is raised to 60° C. whileintroducing a solution of 43.7 g of sodium thiosulfate (in the form ofits pentahydrate) in 15.6 cc of water.

The resulting reaction mixture is maintained at 60° C. for 8 hours. Thenafter cooling, 71 cc of a concentrated aqueous solution of NaOH areadded thereto. The reaction mixture is then left to stand for 2 hours,after which the organic phase is extracted with 100 cc of ethyl acetate.The extract is dried and concentrated under reduced pressure.

By distillation of the residue the expected diamine, BP=140°-150° C.(1.2 mm Hg), is obtained.

In an analogous manner, there have been prepared, in accordance with themethods described above, the di-tertiary diamines indicated in Table Ibelow. These di-tertiary diamines are employed as initial reactants inthe examples illustrating the preparation of polymers of formula I givenhereafter.

                                      TABLE I                                     __________________________________________________________________________    Preparation                                                                         Method                                                                  No.   No.  A.sub.1     R       R.sup.1                                        __________________________________________________________________________    7     2    (CH.sub.2).sub.10                                                                         CH.sub.3                                                                              C.sub.12 H.sub.25                              8     1    (CH.sub.2).sub.3                                                                          CH.sub.3                                                                              C.sub.4 H.sub.9                                9     2    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              C.sub.8 H.sub.17                               10    2    (CH.sub.2).sub.10                                                                         CH.sub.3                                                                              C.sub.8 H.sub.17                               11    1    (CH.sub.2).sub.10                                                                         CH.sub.3                                                                              C.sub.4 H.sub.9                                12    2    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              C.sub.16 H.sub.33                              13    1    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              cyclohexyl                                     14    1    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              isobutyl                                       15    2    (CH.sub.2).sub.3                                                                          CH.sub.3                                                                              C.sub.12 H.sub.25                              16    2    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              C.sub.12 H.sub.25                              17    1    p-xylylidene                                                                              CH.sub.3                                                                              C.sub.4 H.sub.9                                18    1    m-xylylidene                                                                              CH.sub.3                                                                              C.sub.4 H.sub.9                                19    1    (CH.sub.2).sub.12                                                                         CH.sub.3                                                                              C.sub.4 H.sub.9                                20    1    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              C.sub.3 H.sub.7                                21    1    (CH.sub.2).sub.6                                                                          CH.sub.3                                                                              isopropyl                                      22    1    (CH.sub.2).sub.3                                                                          CH.sub.3                                                                              benzyl                                         23    1                                                                                   ##STR33##  CH.sub.3                                                                              C.sub.6 H.sub.13                               24    1    (CH.sub.2).sub.8                                                                          CH.sub.3                                                                              isobutyl                                       25    1                                                                                   ##STR34##  CH.sub.3                                                                              C.sub.8 H.sub.17                               26    1                                                                                   ##STR35##  CH.sub.3                                                                              C.sub.4 H.sub.9                                27                                                                                        ##STR36##  CH.sub.3                                                                              C.sub.10 H.sub.21                              28                                                                                        ##STR37##  CH.sub.3                                                                              C.sub.8 H.sub.17                               29         (CH.sub.2).sub.3                                                                          CH.sub.2 CH.sub.2 OH                                                                  C.sub.12 H.sub.25                              30         (CH.sub.2).sub.6                                                                          CH.sub.2 CH.sub.2 OH                                                                  C.sub.12 H.sub.25                              31         (CH.sub.2).sub.6                                                                          CH.sub.2 CH.sub.2 OH                                                                  C.sub.4 H.sub.9                                32         (CH.sub.2).sub.2SS(CH.sub.2).sub.2                                                        CH.sub.3                                                                              C.sub.12 H.sub.25                              33         (CH.sub.2).sub.2SS(CH.sub.2).sub.2                                                        CH.sub.3                                                                              C.sub.8 H.sub.17                               __________________________________________________________________________

EXAMPLES OF PREPARATION OF POLYMERS OF FORMULA I

In all the examples below, the polymers are isolated, except whereindicated to the contrary, by concentrating the reaction mixture underreduced pressure and drying under vacuum (in the order of 0.1 mm Hg), inthe presence of phosphoric anhydride. In Examples 1-73, the processemployed is process 1a described above.

EXAMPLE 1 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₆, B═(CH₂)₃ andX═Br

There is agitated for 170 hours, at ambient temperature, a solution of:

172.3 g of N,N,N',N'-tetramethyl hexamethylene diamine and

202 g of 1,3-dibromo propane in 650 cc of a 50:50 mixture ofmethanol-dimethylformamide.

On the addition of anhydrous acetone a white precipitate is obtainedwhich is then filtered and dried.

The polymer recovered contains 35.4% Br.

EXAMPLE 2 Polymer of Formula I wherein R═R'═CH₃, A═B═(CH₂)₆ and X═Br

There is heated at reflux for 24 hours, with agitation, the followingsolution:

172.3 g of N,N,N',N'-tetramethyl hexamethylene diamine and

244 g of 1,6-dibromo hexane in 1600 cc of anhydrous methanol.

The polymer obtained contains 36.6% Br and is soluble in water.

EXAMPLE 3 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₂, ##STR38## andX═Br

There is heated at reflux for 50 hours the following mixture:

116.2 g of N,N,N',N'-tetramethyl ethylene diamine and

264 g of p-xylylidene bromide in 3200 cc of anhydrous methanol.

On cooling, a precipitate forms which is then filtered and dried. Theresulting polymer contains 38.8% Br and is soluble in a water-ethanolmixture.

EXAMPLE 4 Polymer of Formula I wherein R═CH₃, R'═C₁₂ H₂₅, A═(CH₂)₃,B═(CH₂)₆ and X═Br

There is heated at reflux for 80 hours the following solution:

438 g of N,N'-didodecyl-N,N'-dimethyl trimethylene diamine and

244 g of 1,6-dibromo hexane in 3200 cc of anhydrous methanol. Theresulting polymer contains 23.4% Br and is soluble in ethanol.

EXAMPLE 5 Polymer of Formula I wherein R═CH₃, R'═C₄ H₉, A═(CH₂)₆,B═(CH₂)₁₀ and X═1813 Br

There is heated at reflux for 45 hours the following solution:

256 g of N,N'-dibutyl-N,N'-dimethyl hexamethylene diamine and

300 of 1,10-dibromo decane in 3200 cc of anhydrous methanol. Theresulting polymer contains 25.0% Br and is soluble in water and ethanol.

EXAMPLE 6 Polymer of Formula I wherein R═CH₃, R'═C₈ H₁₇, A═(CH₂)₁₀,B═(CH₂)₄ and X═Br

There is heated at reflux for 60 hours the following solution:

424 g of N,N'-dimethyl-N,N'-dioctyl decamethylene diamine and

216 g of 1,4-dibromo butane in 3200 cc of anhydrous methanol. Theresulting polymer contains 21.1% Br.

EXAMPLE 7 Polymer of Formula I wherein R═CH₃, R'═C₈ H₁₇, A═(CH₂)₃,B═(CH₂)₄ and X═Br

There is heated at reflux for 60 hours the following solution:

326 g of N,N'-dimethyl-N,N'-dioctyl trimethylene diamine and

216 g of 1,4-dibromo butane.

The polymer obtained contains 26,0% Br.

EXAMPLE 8 Polymer of Formula of Formula I wherein R═CH₃, R'═C₁₂ H₂₅,A═(CH₂)₁₀, B═(CH₂)₄ and X═Br

There is heated at reflux for 80 hours the following solution:

537 g of N,N'-didodecyl-N,N'-dimethyl decamethylene diamine and

216 g of 1,4-dibromo butane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 20,6% Br and is soluble in ethanol.

EXAMPLE 9 Polymer of Formula I wherein R═R'═CH₃, A═B═(CH₂)₁₀ and X═Br

There is heated at reflux for 25 hours the following solution:

225 g of N,N,N',N'-tetramethyl decamethylene diamine and

301 g of 1,10-dibromo decane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 28.0% Br.

EXAMPLE 10 Polymer of Formula I wherein R═CH₃, R'═C₈ H₁₇, A═B═(CH₂)₆ andX═Br

There is heated at reflux for 40 hours the following solution:

368 g of N,N'-dimethyl-N,N'-dioctyl hexamethylene diamine and

244 g of 1,6-dibromo hexane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 24.3% Br.

EXAMPLE 11 Polymer of Formula I wherein R═CH₃, R'═C₄ H₉, A═(CH₂)₃##STR39## and X═Br

there is heated at reflux for 65 hours the following mixture:

214 g of N,N'-dibutyl-N,N'-dimethyl trimethylene diamine and

264 g of p-xylylidene bromide in 1800 cc of methanol. The polymerobtained contains 30.7% Br and is soluble in water and in awater-ethanol mixture.

EXAMPLE 12 Polymer of Formula I wherein R═CH₃, R'═C₄ H₉, A═B═(CH₂)₁₀ andX═Br

There is heated at reflux for 55 hours the following solution:

312 g of N,N'-dibutyl-N,N'-dimethyl decamethylene diamine and

301 g of 1,10-dibramo decane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 32.9% and is soluble in water and in ethanol.

EXAMPLE 13 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₆, B═(CH₂)₄ andX═Br

There is agitated for 170 hours, at ambient temperature, the followingsolution:

172.3 g of N,N,N',N'-tetramethyl hexamethylene diamine and

216 g of 1.4-dibromo butane in 650 cc of a 50:50 mixture of methanol anddimethylformamide. On addition thereto of anhydrous acetone, a whiteprecipitate is obtained which is then filtered and dried. The polymercontains 36.6% Br and is soluble in water.

EXAMPLE 14 Polymer of Formula I wherein R═CH₃, R'═C₄ H₉, A═(CH₂)₃,B═(CH₂)₄ and X═Br

There is heated at reflux for 70 hours, with agitation, the followingsolution:

214.4 g of N,N'-dibutyl-N,N'-dimethyl trimethylene diamine and

216 g of 1,4-dibromo butane in 3600 cc of anhydrous methanol. Thepolymer obtained contains 32.8% Br and is soluble in water and ethanol.

EXAMPLE 15 Polymer of Formula I wherein R═CH₃, R'═C₄ H₉, A═B═(CH₂)₆ andX═Br

There is heated at reflux for 40 hours the following solution:

256 g of N,N'-dibutyl-N,N'-dimethyl hexamethylene diamine and

244 g of 1,6-dibromo bexane in 3600 cc of anhydrous methanol. Thepolymer contains 28.2% Br and is soluble in water and ethanol.

EXAMPLE 16 Polymer of Formula I wherein R═CH₃, R'═C₁₂ H₂₅, A═(CH₂)₆,B═(CH₂)₃ and X═Br

There is heated at reflux for 30 hours the following solution:

480.9 g of N,N'-didodecyl-N,N'-dimethyl hexamethylene diamine and

202 g of 1,3-dibrromo propane in a mixture of 2000 cc of aceonitrile and4000 cc of isopropanol. The polymer formed contains 20.65% Br and issoluble in ethanol and a water-ethanol mixture.

EXAMPLE 17 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₃, B═(CH₂)₆ andX═Br

There is heated at reflux for 55 hours the following solution:

130.2 g of N,N,N',N'-tetramethyl trimethylene diamine and

244 g of 1,6-dibromo hexane.

The polymer formed contains 39.6% Br and is soluble in water andethanol.

EXAMPLE 18 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₂, B═(CH₂)₆ andX═Br

There is heated at reflux for 50 hours the following solution:

116.2 g of N,N,N',N'-tetramethyl ethylene diamine and

244 g of 1,6-dibromo hexane in 3200 cc of anhydrous methanol. Thepolymer contains 41.9% Br and is soluble in water and in a water-ethanolmixture.

EXAMPLE 19 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₂, B═(CH₂)₁₀and X═Br

There is heated at reflux for 60 hours the following solution:

116.2 of N,N,N',N'-tetramethyl ethylene diamine and

300 g of 1,10-dibromo decane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 34.1% Br and is soluble in ethanol and awater-ethanol mixture.

EXAMPLE 20 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₃, ##STR40##and X═Br

There is heated at reflux for 70 hours the following mixture:

130.2 g of N,N,N',N'-tetramethyl trimethylene diamine and

264 g of p-xylylidene bromide in 3200 cc of anhydrous methanol. Thepolymer obtained contains 37.7% Br.

EXAMPLE 21 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₂, B═(CH₂)₄ andX═Br

There is heated at reflux for 50 hours the following solution:

116.2 g of N,N,N',N'-tetramethyl ethylene diamine and

216 g of 1,4-dibromo butane in 3200 cc of anhydrous methanol. Thepolymer formed contains 45.8% Br and is soluble in water and in awater-ethanol mixture.

EXAMPLE 22 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₃, B═(CH₂)₄ andX═Br

There is heated at reflux for 55 hours the following solution:

130.2 g of N,N,N',N'-tetramethyl trimethylene diamine and

216 g of 1,4-dibromo butane in 3200 cc of anhydrous methanol. Thepolymer formed contains 46.2% Br and is soluble in water and ethanol.

EXAMPLE 23 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₆, ##STR41##and X═Br

The following mixture is heated at reflux for 1 hour:

172.3 g of N,N,N',N'-tetramethyl hexamethylene diamine and

264 g of p-xylylidene bromide in 3200 cc of anhydrous methanol. Aftercooling the precipitate which has formed is filtered and dried. Thepolymer contains 34.6% Br and is soluble in water.

EXAMPLE 24 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₆, B═(CH₂)₁₀and X═Br

The following solution is heated at reflux for 15 hours:

172.3 g of N,N,N',N'-tetramethyl hexamethylene diamine and

300 g of 1,10-dibromo decane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 32.7% Br and is soluble in water and ethanol.

EXAMPLE 25 Polymer of Formula I wherein R═CH₃, R'═C₄ H₉, A═(CH₂)₃,B═(CH₂)₁₀ and X═Br

The following solution is heated at reflux for 70 hours:

214.4 g of N,N'-dibutyl-N,N'-dimethyl trimethylene diamine and

300 g of 1,10-dibromo decane in 3200 cc of anhydrous methanol. Thepolymer obtained contains 27.3% Br and is soluble in ethanol and in awater-ethanol mixture.

EXAMPLE 26 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₃, B═(CH₂)₁₀and X═Br

The following solution is heated at reflux for 38 hours:

130.2 g of N,N,N',N'-tetramethyl trimethylene diamine and

300 g of 1,10-dibromo decane in 3200 cc of anhydrous methanol. Thepolymer formed contains 34.3% Br and is soluble in water and in ethanol.

EXAMPLE 27 Polymer of Formula I wherein R═CH₃, R'═C₁₂ H₂₅, A═(CH₂)₆,B═(CH₂)₄ and X═Br

The following solution is heated for 12 hours at 85° C.:

480.9 g of N,N'-didodecyl-N,N'-dimethyl hexamethylene diamine and

216 g of 1,4-dibromo butane in a mixture of 2000 cc of acetonitrile and4000 cc of isopropanol. The polymer formed contains 20.4% Br and issoluble in ethanol.

EXAMPLE 28 Polymer of Formula I wherein R═CH₃, R'═C₁₂ H₂₅, A═(CH₂)₆,B═(CH₂)₅ and X═Br

The following solution is heated for 28 hours at 85° C.:

480.9 g of N,N'-didodecyl-N,N'-dimethyl hexamethylene diamine and

230 g of 1,5-dibromo pentane in a mixture of 2000 cc of acetonitrile and4000 cc of isopropanol. The polymer formed contains 19.9% Br and issoluble in ethanol.

By operating in accordance with methods analogous to those described inthe preceding examples, there have been obtained, by Process 1 definedabove, polymers of Formula I whose structure is indicated in Table IIbelow.

                                      TABLE II                                    __________________________________________________________________________    Ex.                                                Soluble                    n.sup.o                                                                           A                 B            R    R.sup.1 X  in                         __________________________________________________________________________    29  (CH.sub.2).sub.6  (CH.sub.2).sub.5                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water                      30  (CH.sub.2).sub.6  (CH.sub.2).sub.6                                                                           CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol water-ethanol      31  (CH.sub.2).sub.6  (CH.sub.2).sub.10                                                                          CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol water-ethanol      32  (CH.sub.2).sub.3  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol                    33  (CH.sub.2).sub.3  (CH.sub.2).sub.10                                                                          CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol                    34  (CH.sub.2).sub.10 (CH.sub.2).sub.10                                                                          CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol                    35  (CH.sub.2).sub.6  p-xylylidene CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol                    36  (CH.sub.2).sub.10 p-xylylidene CH.sub.3                                                                           C.sub.12 H.sub.25                                                                     Br ethanol                    37  (CH.sub.2).sub.5  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.10 H.sub.21                                                                     Br ethanol water-ethanol      38  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.16 H.sub.33                                                                     Br ethanol                    39  (CH.sub.2).sub.3  (CH.sub.2).sub.10                                                                          CH.sub.3                                                                           C.sub.8 H.sub.17                                                                      Br ethanol                    40  (CH.sub.2).sub.6  (CH.sub.2).sub.10                                                                          CH.sub.3                                                                           C.sub.8 H.sub.17                                                                      Br ethanol                    41  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           cyclohexyl                                                                            Br water-ethanol,ethanol      42  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           iso-C.sub.4 H.sub.9                                                                   Br water-ethanol,ethanol      43  (CH.sub.2).sub.6                                                                                 ##STR42##   CH.sub.3                                                                           CH.sub.3                                                                              Br water,  water-                                                                ethanol,  ethanol          44  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           iso-    Br water,                                                             C.sub.3 H.sub.7                                                                       water-                                                                           ethanol                    45  (CH.sub.2).sub.3  (CH.sub.2).sub.6                                                                           CH.sub.3                                                                           benzyl  Br ethanol,                                                                      water-                                                                        ethanol                    46  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.4 H.sub.9                                                                       Br water,water-                                                                  ethanol,                                                                      ethanol                    47  (CH.sub.2).sub.6 + 1.6%                                                                         (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water,                         by weight of                                   water-                         terminal                                       ethanol                        groups:                                                                       N(C.sub.2 H.sub.5).sub.3                                                  48  (CH.sub.2).sub.6 + 2.8%                                                                         (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water,                         by weight of                                   water-                         terminal                                       ethanol                        groups:                                                                       N(C.sub.2 H.sub.5).sub.3                                                  49  (CH.sub.2).sub.6 + 7.4%                                                                         (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water,                         by weight of                                   water-                         terminal                                       ethanol                        groups:                                                                       N(C.sub.2 H.sub.5).sub.3                                                  50  (CH.sub.2).sub.6  (CH.sub.2).sub.4                                                                           CH.sub.3                                                                           C.sub.10 H.sub.21                                                                     Br ethanol                    51  (CH.sub.2).sub.6  p-xylylidene CH.sub.3                                                                           C.sub.10 H.sub.21                                                                     Br ethanol                    52  p-xylylidene      (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.4 H.sub.9                                                                       Br ethanol,                                                                      water-                                                                        ethanol                    53  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                          Br water,                                                                        water-                                                                        ethanol                    54  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           benzyl  Br water,water-                                                                  ethanol,                                                                      ethanol                    55  m-xylylidene      (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.4 H.sub.9                                                                       Br water,water-                                                                  ethanol,                                                                      ethanol                    56  (CH.sub.2).sub.8  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           iso-    Br water-                                                             C.sub.4 H.sub.9                                                                          ethanol,                                                                      ethanol                    57  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.7                                                                       Br water,water-                                                                  ethanol                    58  (CH.sub.2).sub.12 (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           C.sub.4 H.sub.9                                                                       Br water,water-                                                                  ethanol,                                                                      ethanol                    59  (CH.sub.2).sub.6  o-xylylidene CH.sub.3                                                                           C.sub.8 H.sub.17                                                                      Br ethanol                    60  (CH.sub.2).sub.6  o-xylylidene CH.sub.3                                                                           CH.sub.3                                                                              Br water,water-                                                                  ethanol                    61  (CH.sub.2).sub.6  (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              I  water,water-                                                                  ethanol                    62  (CH.sub.2).sub.10 (CH.sub.2).sub.3                                                                           (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                          Br water,water-                                                                  ethanol,                                                                      ethanol                    63  (CH.sub.2).sub.6                                                                                 ##STR43##   CH.sub.3                                                                           CH.sub.3                                                                              Br water,water-  ethanol,                                                        ethanol                    64  (CH.sub.2).sub.10 (CH.sub.2).sub.4                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water,water-                                                                  ethanol,                                                                      ethanol                    65  (CH.sub.2).sub.6                                                                                 ##STR44##   CH.sub.3                                                                           CH.sub.3                                                                              Br water,water-  ethanol,                                                        ethanol                    66                                                                                 ##STR45##        (CH.sub.2).sub.6                                                                           CH.sub.3                                                                           C.sub.6 H.sub.13                                                                      Br ethanol                    67  (CH.sub.2).sub.3  (CH.sub.2).sub.6                                                                           (CH.sub.2O(CH.sub.2).sub.2                                                                 Br water,water-                                                                  ethanol                    68  (CH.sub.2).sub.5  (CH.sub.2).sub.7                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water,water-                                                                  ethanol,                                                                      ethanol                    69  (CH.sub.2).sub.5  (CH.sub.2).sub.9                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water,                                                                        water-                                                                        ethanol                    70                                                                                 ##STR46##        (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br ethanol                    71                                                                                 ##STR47##        (CH.sub.2).sub.6                                                                           CH.sub.3                                                                           C.sub.8 H.sub.17                                                                      Br ethanol                    72                                                                                 ##STR48##        (CH.sub.2).sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              Br water-ethanol  ethanol                                                        7                          73                                                                                 ##STR49##        (CH.sub.2).sub.6                                                                           CH.sub.3                                                                           C.sub.4 H.sub.9                                                                       Br ethanol                    __________________________________________________________________________

EXAMPLE 74 Polymer of Formula I wherein R═R'═CH₃, A═B═(CH₂)₁₀ and X═Br

50 g of 10-bromo decyl dimethylamine hydrobromide prepared in accordancewith the disclosure of M. R. Lehman, C. D. Thompson and C. S. Marvel,J.A.C.S. 55, 1977 (1933) are dissolved in 200 cc of water. There isthen, added a 25% aqueous solution of NaOH until the pH thereof is 12.The mixturte is then extracted with chloroform and the extract isevaporated to dryness. The resulting residue is dissolved in 250 cc ofmethanol and the resulting solution is heated at reflux for 24 hours.

On addition of ethyl acetate, a precipitate of the polymer formed isobtained which contains 27.8% Br.

The polymer is soluble in water and in ethanol and is practicallyidentical to the product described in Example 9 above.

The 10-bromodecyl dimethylamine hydrobromide used as an initial reactantis obtained in the following manner: 12.6 g of 10-phenoxy decyldimethylamine is dissolved in 63 cc of a 48% aqueous solution of HBr.The resulting solution is heated to 150° C. and distilled underatmospheric pressure until the temperature of the vapors reaches 125° C.There are then added 63 cc of 48% HBr and the distillation is resumeduntil 110 cc of distillate have been obtained. The residue is evaporatedto dryness under reduced pressure and the hydrobromide obtained ispurified by crystallization in an ethanol-ether mixture.

EXAMPLE 75 Polymer of Formula I wherein R═R'═CH₃, A═(CH₂)₆, B═CH₂--CHOH--CH₂ and X═Cl Process 1a

The following solutioln is heated at reflux for 50 hours:

172.3 g of N,N,N',N'-tetramethyl hexamethylene diamine,

129 g of 1,3-dichloro propanol-2 and 3200 cc of acetonitrile.

The polymer obtained contains 19.3% of Cl and is soluble in water andethanol.

EXAMPLE 76 Polymer of Formula I wherein R═R'═CH₃, A═--(CH₂)₃ --,B═--(CH₂)₂ --O--(CH₂)₂ -- and X═Cl Process 1a

The following mixture is heated, with agitation, at 100° C. for 32hours:

130 g of N,N,N',N'-tetramethyl trimethyl diamine, 143 g of 2,2'-dichlorodiethylether and

3200 cc of dimethyl formamide.

The precipitated polymer is filtered, washed with anhydrous acetone anddried. It contains 21.5% Cl and is soluble in water.

EXAMPLE 77 Polymer of Formula I wherein R'═CH₃, R═--CH₂ --CH₂ OH,A═(CH₂)₆, B═(CH₂)₃ and X═Br Process 1a

The following solution is heated at reflux for 170 hours:

232.3 g of N,N'-dihydroxyethyl-N,N'-dimethyl hexamethylene diamine,

202 g of 1,3-dibromo propane and 3200 cc of methanol.

The polymer obtained contains 31.5% Br and is soluble in water and in a50:50 mixture of water and ethanol.

EXAMPLE 78 Polymer of Formula I wherein R═R'═CH₃, A═--(CH₂)₂--S--S--(CH₂)₂ --, B═(CH₂)₅ and X═Br Process 1a

The following mixture is heated for 30 hours at 95° C., with agitation:

208.4 g of N,N-dimethyl 2-amino ethyl disulfide,

230 g of 1,5-dibromo pentane and

3200 cc of dimethyl formamide.

The polymer obtained contains 33.8% Br and is soluble in water and in a50:50 water-ethanol mixture.

EXAMPLE 79 Polymer of Formula I wherein R═R'═(CH₂)₂ --O--(CH₂)₂, B═CH₂--CHOH--CH₂, A═(CH₂)₆ and X═Br Process 1b

The following solution is heated at reflux for 300 hours:

230.3 g of 1,3-dimorpholino propanol-2,

244 g of 1,6-dibromo hexane and

3200 cc of methanol.

The polymer obtained contains 30.0% Br and is soluble in water and in a50:50 mixture of water and ethanol.

EXAMPLE 80 Polymer of Formula I wherein R═R'═CH₃, ##STR50## B═(CH₂)₃ andX═Br Process 1a

The following solution is heated at reflux for 26 hours:

254 g of 4,4'-N,N,N',N'-tetramethyl diamino diphenyl methane,

202 g of 1,3-dibromo propane,

900 cc of dimethyl formamide and

900 cc of methanol.

The methanol is evaporated and 2000 cc of anhydrous acetone are addedthereto. The resulting mixture is cooled and the polymer formed isfiltered therefrom. The polymer contains 25.8% Br and is soluble inwater and in a 50:50 mixture of water and ethanol.

EXAMPLE 81 Polymer of Formula I wherein R═R'═CH₃, A═--(CH₂)₂ --O--(CH₂)₂--, B═--CH₂ --C₆ H₄ --CH₂ --(para) and X═Br Process 1a

The following solution is heated at reflux for 60 hours:

160.3 g of 2,2'-bis(dimethylamino) diethyl ether,

264 g of p-xylylidene bromide,

1000 cc of acetonitrile and

4000 cc of isopropanol.

The polymer obtained contains 33.8 % Br and is soluble in water and in a50:50 mixture of water and ethanol.

In an analogous fashion, the quaternized polymers identified in TableIII, below, have been prepared.

                                      TABLE III                                   __________________________________________________________________________    Ex.                                                        Pro-               no R      R'  A                B             X Soluble in  cess               __________________________________________________________________________    82 CH.sub.2 CH.sub.2 OH                                                                 CH.sub.3                                                                          (CH.sub.2).sub.3 (CH.sub.2).sub.6                                                                            Br                                                                              Water, water-ethanol                                                                      1a                 83 "      CH.sub.3                                                                          "                (CH.sub.2).sub.10                                                                           Br                                                                              Water       1a                 84 "      C.sub.8 H.sub.17                                                                  "                CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              Ethanol,                                                                                  1ater-ethanol      85 "      "   "                                                                                               ##STR51##    Br                                                                              Ethanol     1a                 86 "      C.sub.12 H.sub.25                                                                 (CH.sub.2).sub.6 (CH.sub.2).sub.3                                                                            Br                                                                              "           1a                 87 "      CH.sub.3                                                                          (CH.sub.2).sub.10                                                                              "             Br                                                                              Ethanol,                                                                                  1ater-ethanol      88 "      CH.sub.3                                                                           ##STR52##       (CH.sub.2).sub.6                                                                            Br                                                                              "           1a                 89 "      C.sub.4 H.sub.9                                                                   (CH.sub.2).sub.6 (CH.sub.2).sub.2O(CH.sub.2                                                                  Brsub.2                                                                         Ethanol,                                                                                  1ater-ethanol      90 "      CH.sub.3                                                                          (CH.sub.2).sub.3 CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              Water, water-ethanol                                                                      1b                 91 CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.2SS(CH.sub.2).sub.2                                                             (CH.sub.2).sub.3                                                                            Br                                                                              "           1a                 92 CH.sub.3                                                                             C.sub.8 H.sub.17                                                                  "                "             Br                                                                              Ethanol water-ethanol                                                                     1a                 93 CH.sub.3                                                                             CH.sub.3                                                                          "                (CH.sub.2).sub.4                                                                            Br                                                                              Water, water-ethanol                                                                      1*                 94 CH.sub.3                                                                             CH.sub.3                                                                          "                (CH.sub.2).sub.6                                                                            Br                                                                              "           1a                 95 CH.sub.3                                                                             C.sub.12 H.sub.25                                                                 "                "             Br                                                                              Ethanol,                                                                                  1ater-ethanol      96 CH.sub.3                                                                             CH.sub.3                                                                          "                CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              Water, water-ethanol                                                                      1a                 97 CH.sub.3                                                                             CH.sub.3                                                                          "                (CH.sub.2).sub.10                                                                           Br                                                                              "           1a                 98 CH.sub.3                                                                             CH.sub.3                                                                          "                (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                           Br                                                                              "           1a                 99 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                   "                                                                                               ##STR53##    Br                                                                              "           1a                 100                                                                              CH.sub.3                                                                             CH.sub.3                                                                           (CH.sub.2).sub.2SS(CH.sub.2).sub.2                                                             ##STR54##    Br                                                                              Water, water-ethanol                                                                      1a                 101                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.3SS(CH.sub.2).sub.3                                                             (CH.sub.2).sub.3                                                                            Br                                                                              "           1a                 102                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                              (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                           Br                                                                              "           1a                 103                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.3O(CH.sub.2).sub.3                                                              (CH.sub.2).sub.3                                                                            Br                                                                              "           1a                 104                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.3O(CH.sub.2).sub.2                                                              CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              "           1b                 105                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.3 CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              "           1b                 106                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.4 CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              Water       1b                 107                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.5 CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              Water, water-ethanol                                                                      1b                 108                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.6 "             Br                                                                              "           1b                 109                                                                              (CH.sub.2).sub.5                                                                         (CH.sub.2).sub.6 "             Br                                                                              Water, ethanol                                                                            1b                 110                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.10                                                                              "             Br                                                                              "           1b                 111                                                                              CH.sub.3                                                                             CH.sub.3                                                                           ##STR55##       "             Br                                                                              Water, water-ethanol                                                                      1b                 112                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                              (CH.sub.2).sub.3                                                                            Br                                                                              "           1a                 113                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.2SO(CH.sub.2).sub.2                                                             (CH.sub.2).sub.3                                                                            Br                                                                              "           1a                 114                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.2SO.sub.2(CH.sub.2).sub.2                                                       (CH.sub.2).sub.6                                                                            Br                                                                              "           1a                 115                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.6 CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              "           1a                 116                                                                              CH.sub.3                                                                             C.sub.4 H.sub.9                                                                   (CH.sub.2).sub.10                                                                              CH.sub.2CHOHCH.sub.2                                                                        Br                                                                              Water, ethanol                                                                            1a                 117                                                                              CH.sub.3                                                                             C.sub.4 H.sub.9                                                                    ##STR56##       (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                           Br                                                                              Water, water-ethanol                                                                      1a                 118                                                                              CH.sub.3                                                                             C.sub.12 H.sub.25                                                                 (CH.sub.2).sub.3 "             Br                                                                              Ethanol     1a                 119                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.6 "             Cl                                                                              Water, water-ethanol                                                                      1a                 120                                                                              CH.sub.3                                                                             C.sub.8 H.sub.17                                                                  (CH.sub.2).sub.6 "             Br                                                                              Ethanol,                                                                                  1ater-ethanol      121                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.4 (CH.sub.2).sub.7                                                                            Br                                                                              Water, ethanol                                                                            1a                 122                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.4 (CH.sub.2).sub.9                                                                            Br                                                                              "           1a                 123                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.4                                                                                ##STR57##    Br                                                                              Water       1a                 124                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.5                                                                                ##STR58##    Br                                                                              Water, ethanol                                                                            1a                 125                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                              (CH.sub.2).sub.3                                                                            Br                                                                              Water       1a                 126                                                                              CH.sub.3                                                                             CH.sub.3                                                                           ##STR59##                                                                                      ##STR60##    Br                                                                              Ethanol     1a                 127                                                                              CH.sub.3                                                                             CH.sub.3                                                                           ##STR61##       (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                           Br                                                                              Water, ethanol                                                                            1a                 128                                                                              (CH.sub.2).sub.5                                                                          ##STR62##                                                                                      ##STR63##    Br                                                                              Water       1b                 129                                                                              (CH.sub.2).sub.5                                                                          ##STR64##                                                                                      ##STR65##    Br                                                                              Water       1b                 130                                                                              CH.sub.3                                                                             iso (CH.sub.2).sub.3 (CH.sub.2).sub.7                                                                            Br                                                                              Water, ethanol                                                                            1a                           C.sub.3 H.sub.7                                                     131                                                                              CH.sub.3                                                                             iso (CH.sub.2).sub.3 (CH.sub.2).sub.3                                                                            Br                                                                              Water       1a                           C.sub.3 H.sub.7                                                     132                                                                              CH.sub. 3                                                                            C.sub.3 H.sub.7                                                                   (CH.sub.2).sub.6                                                                                ##STR66##    Br                                                                              Water       1a                 133                                                                              CH.sub.3                                                                             C.sub.3 H.sub.7                                                                   (CH.sub.2).sub.6                                                                                ##STR67##    Br                                                                              ethanol     1a                 134                                                                              CH.sub.3                                                                             benzyl                                                                            (CH.sub.2).sub.3                                                                                ##STR68##    Br                                                                              Water, ethanol                                                                            1a                 135                                                                              CH.sub.3                                                                             "   (CH.sub.2).sub.6                                                                                ##STR69##    Cl                                                                              Ethanol     1a                 136                                                                              CH.sub.3                                                                             C.sub.4 H.sub.9                                                                    ##STR70##                                                                                      ##STR71##    Br                                                                              Water       1a                 137                                                                              CH.sub.3                                                                             CH.sub.3                                                                           ##STR72##                                                                                      ##STR73##    Br                                                                              Water, ethanol                                                                            1a                 138                                                                              CH.sub.3                                                                             C.sub.3 H.sub.7                                                                    ##STR74##       (CH.sub.2).sub.10                                                                           Br                                                                              "           1a                 139                                                                              CH.sub. 3                                                                            C.sub.3 H.sub.7                                                                   (CH.sub.2).sub.3 (CH.sub.2).sub.4                                                                            Br                                                                              "           1a                 140                                                                              CH.sub.3                                                                             C.sub.3 H.sub.7                                                                   (CH.sub.2).sub.6 (CH.sub.2).sub.4                                                                            Br                                                                              "           1a                 141                                                                              CH.sub.3                                                                             CH.sub.3                                                                          (CH.sub.2).sub.3 (CH.sub.2).sub.6                                                                            Cl                                                                              "           1a                 __________________________________________________________________________

EXAMPLES OF COSMETIC COMPOSITIONS AND TREATMENTS EXAMPLE I Hand TreatingCream

1. The following cream is prepared:

    ______________________________________                                        Vaseline oil            10     g                                              Cetyl alcohol           6      g                                              Glyceryl monostearate --                                                                              4      g                                              self-emulsifying                                                              Triethanolamine         2      g                                              Methyl p-hydroxy benzoate                                                                             0.1    g                                              Polymer of Example 1    4      g                                              Water, q.s.p.           100    g                                              ______________________________________                                    

This cream is applied to the hands with rubbing so as to achieve goodpenetration. The hands are soft and have a pleasant feel.

2. Analogous results are obtained by replacing in the above hand creamcomposition, the 4 g of the polymer of Example 1 by 3.5 g of the polymerof Example 15.

EXAMPLE II Oxidation Hair Dye Cream Support

1. The following cream is prepared:

    ______________________________________                                        Cetyl stearyl alcohol   20     g                                              Oleic diethanolamide    4      g                                              Sodium cetyl stearyl sulfate                                                                          3      g                                              Polymer of Example 15   5      g                                              Ammonia, 22° Be (11N)                                                                          10     ml                                             M-diamino anisol sulfate                                                                              0.048  g                                              Resorcin                0.420  g                                              M-amino phenol base     0.150  g                                              Nitro-p-phenylene diamine                                                                             0.085  g                                              p-toluylene diamine     0.004  g                                              Trilon B--tetrasodium salt                                                                            1      g                                              ethylene diamine tetra-                                                       acetic acid                                                                   Sodium bisulfite, d = 1.32                                                                            1.200  g                                              Water, q.s.p.           100    g                                              ______________________________________                                    

30 g of this cream are mixed with 45 g of H₂ O₂ (20 volumes) thusproducing a glossy, thick, pleasant to apply cream which adheres well tothe hair. This cream is permitted to remain in contact with the hair for30 minutes, after which the hair is rinsed and dried. When so applied to100% white hair, a blond coloration is obtained and the hair, wet ordry, is easy to untangle and has a shiny appearance, and a pleasant andsilky feel.

2. The following cream is prepared:

    ______________________________________                                        Cetyl stearyl alcohol   20     g                                              Oleic diethanolamide    4      g                                              Sodium cetyl stearyl sulfate                                                                          3      g                                              Polymer of Example 3    5      g                                              Ammonia, 22° Be (11N)                                                                          12     ml                                             M-diamino anisol sulfate                                                                              0.048  g                                              Resorcin                0.420  g                                              M-amino phenol base     0.150  g                                              Nitro p-phenylene diamine                                                                             0.085  g                                              P-toluylene diamine     0.004  g                                              Trilon B                1      g                                              Sodium bisulfite, d = 1.32                                                                            1.200  g                                              Water, q.s.p.           100    g                                              ______________________________________                                    

30 g of this cream are mixed with 45 g of H₂ O₂ (20 volumes) thusproducing a glossy, thick and pleasant to apply cream which adheres wellto the hair. The cream is permitted to remain in contact with the hairfor 30 minutes, after which the hair is rinsed and dried. When soapplied to 100% white hair, a blond coloration is achieved. The hair,wet or dry, is easy to untangle and has a shiny appearance and apleasant and silky feel.

EXAMPLE III Hair Setting Lotions for Sensitized Hair

1. An alcoholic lotion is prepared as follows:

    ______________________________________                                        Polyvinylpyrrolidone   1      g                                               (MW 40,000)                                                                   Polymer of Example 7   1      g                                               Ethyl alcohol, q.s.p.  100    ml                                              ______________________________________                                    

The resulting lotion is applied to the hair which is then set in thedesired style and dried. The hair is hard and plasticized, is shiny andhas body, and has a silky feel and is easily untangled.

2. Analogous results are obtained by replacing in the above compositionthe polymer of Example 7 by the polymer of Example 16.

3. The following lotion is prepared:

    ______________________________________                                        Polymer of Example 18    0.8    g                                             Copolymer of vinylpyrrolidone/                                                                         1.0    g                                             vinyl acetate, 60:40 K value                                                  (1% ethanol solution) = 25-35                                                                          1.0    g                                             Triethanolamine, q.s.p.  pH     6                                             Water, q.s.p.            100    ml                                            ______________________________________                                    

The composition is applied to bleached hair which is then set and dried.The results achieved are analogous to those obtained in the precedingexample.

4. The following lotion is prepared:

    ______________________________________                                        Polymer of Example 19    1      g                                             Copolymer of vinylpyrrolidone/                                                                         1      g                                             vinyl acetate, 60/40 K value                                                  (1% ethanol solution) = 25-35                                                 Ethyl alcohol, q.s.p. 50°                                              Triethanolamine, q.s.p.  pH     7                                             Water, q.s.p.            100    ml                                            ______________________________________                                    

The lotion is applied to bleached hair which is then set and dried.Results analogous to those achieved in the preceding example areobtained.

5. The following lotion is prepared:

    ______________________________________                                        Polymer of Example 17   1.5    g                                              Copolymer of vinyl acetate/                                                                           1.5    g                                              crotonic acid, 90:10,                                                         MW = 20,000                                                                   Triethanolamine, q.s.p. pH     7.5                                            Water, q.s.p.           100    ml                                             ______________________________________                                    

This lotion is applied to bleached hair which is then set and dried.Results analogous to those achieved in the preceding example areobtained.

6. The following composition is prepared:

    ______________________________________                                        Polymer of Example 2  1.59                                                    Copolymer of vinyl acetate/                                                                         1.59                                                    crotonic acid, 90:10 MW = 20,000                                              Monoethanolamine, q.s.p.                                                                            pH 7                                                    Water, q.s.p.         100 ml                                                  ______________________________________                                    

This composition is applied to bleached hair which is then set anddried. Results analogous to those obtained in the preceding example areattained.

EXAMPLE IV Hail Treating Lotions - Application With Rinsing

1. 30 ml of the following lotion are applied to wet, clean hair:

    ______________________________________                                        Polymer of Example 20   5      g                                              Monoethanolamine, q.s.p.                                                                              pH     7.5                                            Water, q.s.p.           100    ml                                             ______________________________________                                    

This lotion is permitted to remain in contact with the hair for 5minutes, after which the hair is rinsed. The hair has a soft feel and iseasy to untangle. The hair is then set and dried. The dry hair untangleseasily and is shiny and lively and has body.

2. 25 ml of the following lotion are applied to wet, clean hair:

    ______________________________________                                        Polymer of Example 12  6      g                                               Citric acid, q.s.p.    pH     6                                               Water, q.s.p.          100    ml                                              ______________________________________                                    

The lotion is permitted to remain in contact with the hair for 5minutes, after which the hair is rinsed. The hair has a soft feel and iseasy to untangle. The hair is then set and dried. The dry hair is easyto untangle, is shiny and lively and has body.

3. 25 ml of the following lotion are applied to wet, clean hair:

    ______________________________________                                        Polymer of Example 21  6      g                                               Triethanolamine, q.s.p.                                                                              pH     6                                               Water, q.s.p.          100    ml                                              ______________________________________                                    

This lotion is permitted to remain in contact with the hair for 5minutes, after which the hair is rinsed. The hair has a soft feel and iseasy to comb. The hair is then set and dried. The dry hair is easy tocomb, is shiny and lively and has body.

4. 30 ml of the following lotion having a pH of about 7 are applied towet, clean hair:

    ______________________________________                                        Polymer of Example 22  7      g                                               Water, q.s.p.          100    ml                                              ______________________________________                                    

This lotion is permitted to remain in contact with the hair for 5minutes, after which the hair is rinsed. The hair has a soft feel and iseasy to comb. The hair is then set and dried. The dry hair is easy tocomb, is shiny and lively and has body.

5. 25 ml of the following lotion are applied to wet, clean hair:

    ______________________________________                                        Polymer of Example 23   5 g                                                   Monoethanolamine, q.s.p.                                                                              pH 5                                                  Water, q.s.p.           100 ml.                                               ______________________________________                                    

This lotion is permitted to remain in contact with the hair for 5minutes, after which it is rinsed. The hair has a soft feel and is easyto untangle. The hair is then set and dried. The dry hair is easy tocomb, is shiny and lively and has body.

EXAMPLE V Hair Restructuring Lotion - Application Without Rinsing

1. Before use of 0.3 g of N,N'-di-(hydroxymethyl) ethylene thiourea,hereinafter called compound A, is mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 11   0.6 g                                                 HCl, q.s.p.             pH 2.7                                                Water, q.s.p.           100 ml                                                ______________________________________                                    

This mixture is applied to washed and dried hair before setting thesame. The hair combs easily and has a silky feel. The hair is then setand dried. The hair is shiny, lively and has body. It has a silky feeland combs easily.

2. Before use 0.4 g of compound A is mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 14   0.25 g                                                Phosphoric acid, q.s.p. pH 2.7                                                Water, q.s.p.           100 ml                                                ______________________________________                                    

This mixture is applied to washed and dried hair before being set. Thehair combs easily and has a silky feel. The hair is then set and dried.The hair is shiny and lively, has body, has a silky feel and is easy tocomb.

3. Before use, 0.5 g of compound A is mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 24   0.6 g                                                 Phosphoric acid, q.s.p. pH 3                                                  Water, q.s.p.           100 ml                                                ______________________________________                                    

This mixture is applied to washed and dried hair before being set. Thehair combs easily and has a silky feel. The hair is set and dried. Thehair is shiny and lively, has body, has a silky feel and combs easily.

4. Before use, 0.6 g of compound A is mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 13   0.7 g                                                 HCl, q.s.p.             pH 3                                                  Water, q.s.p.           100 ml                                                ______________________________________                                    

This lotion is applied to washed and dried hair before being set. Thehair is easily untangled and has a silky feel. The hair is then set anddried. The hair is shiny and lively, has body, has a silky feel andcombs easily.

5. Before use, 0.5 g of compound A is mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 1    0.5 g                                                 Phosphoric acid, q.s.p. pH 3                                                  Water, q.s.p.           100 ml                                                ______________________________________                                    

This lotion is applied to washed and dried hair before being set. Thehair is easy to untangle and has a silky feel. The hair is then set anddried. The hair is shiny and lively, has body, has a silky feel andcombs easily.

EXAMPLE VI Hair Structuring Lotion - Application With Rinsing

1. Before use, 2 g of compound A are mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 25   5 g                                                   HCl, q.s.p.             pH 2.5                                                Water, q.s.p.           100 ml                                                ______________________________________                                    

This solution is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair is easy to comb, is shinyand lively and has body.

2. Before use, 1.8 g of compound A are mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 26   6 g                                                   Phosphoric acid, q.s.p. pH 3                                                  Water, q.s.p.           100 ml                                                ______________________________________                                    

This lotion is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair combs easily, is shiny andlively and has body.

3. Before use, 1.5 g of compound A are mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 13   4 g                                                   HCl, q.s.p.             pH 3                                                  Water, q.s.p.           100 ml                                                ______________________________________                                    

This lotion is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair combs easily, is shiny andlively and has body.

4. Before use, 2 g of compound A are mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 1    5 g                                                   Phosphoric acid, q.s.p. pH 2.8                                                Water, q.s.p.           100 ml                                                ______________________________________                                    

This lotion is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair combs easily, is shiny andlively and has body.

5. Before use, 1.5 g of compound A are mixed with 25 ml of the followingsolution:

    ______________________________________                                        Polymer of Example 11   5.5 g                                                 Phosphoric acid, q.s.p. pH 3                                                  Water, q.s.p.           100 ml                                                ______________________________________                                    

This lotion is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair is easily combed, is shinyand lively and has body.

EXAMPLE VII Shampoo Compositions

1. The following shampoo composition is prepared:

    ______________________________________                                        C.sub.11 -C.sub.14 α-diol condensed                                                             17 g                                                  with 3-4 moles of glycidol                                                    Polymer of Example 1    3 g                                                   Lactic acid, q.s.p.     pH 3.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

When applied to the head, this clear solution produces a sufficientlymild and abundant foam and facilitates untangling wet hair. Afterrinsing and drying, the hair is lively, light and shiny.

2. The following shampoo composition is prepared:

    ______________________________________                                        Lauryl ether condensed with                                                                           15 g                                                  4 moles of glycerol                                                           Polymer of Example 1    2 g                                                   Tertiary stearyl amine  1.5 g                                                 polyoxyethylenated with                                                       5 moles of ethylene oxide                                                     Lactic acid, q.s.p.     pH 4.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

When applied to the hair, this clear solution produces a mild andabundant foam which is easily removed by rinsing. The hair is veryeasily untangled and after drying exhibits a puffed appearance andliveliness while remaining soft and easy to style.

3. The following shampoo composition is prepared:

    ______________________________________                                        C.sub.11 -C.sub.14 α-diol condensed with                                                        17 g                                                  3-4 moles of glycidol                                                         Polymer of Example 12   3 g                                                   Lactic acid, q.s.p.     pH 3.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

When applied to the head, this clear solution produces a sufficientlymild and abundant foam and improves the untangling of wet hair. Afterdrying, the hair is soft, shiny and has a light appearance.

EXAMPLE VIII Antipellicular Untangling Lotions

1. The following solution is prepared:

    ______________________________________                                        Bis-(2-pyridyl-1-oxide)  0.5 g                                                magnesium disulfide, sold                                                     under the name                                                                "Omadine MDS"                                                                 Polymer of Example 1     0.7 g                                                Copolymer of vinylpyrrolidone/                                                                         1 g                                                  vinyl acetate, 70/30, K value                                                 (1% ethanol solution) = 30-50                                                 KOH, q.s.p.              pH 5.5                                               Water, q.s.p.            100 cc                                               ______________________________________                                    

When applied to the hair, this lotion, in addition to its antipellicularactivity, facilitates the untangling of the hair.

2. The following lotion is prepared:

    ______________________________________                                        (4-ethyl-benzyl alkyl    1 g                                                  dimethyl) ammonium chloride,                                                  wherein the alkyl moiety                                                      is a C.sub.12 -C.sub.14 -C.sub.16 -C.sub.18 mixture                           Polymer of Example 1     0.7 g                                                Copolymer of vinylpyrrolidone/                                                                         1 g                                                  vinyl acetate, 70/30, K value                                                 (1% ethanol solution) = 30-50                                                 KOH, q.s.p.              pH 5.5                                               Water, q.s.p.            100 cc                                               ______________________________________                                    

The application of this lotion, which causes a significant reduction ofpellicles after a few weeks, also provides easy untangling of the hair.

EXAMPLE IX Daily Anti-dandruff Untangling Lotions

The following lotion is prepared:

    ______________________________________                                        Carboxy methyl cysteine 0.3 g                                                 Polymer of Example 7    0.6 g                                                 Cationic polyglucosic   0.3 g                                                 derivative sold under the                                                     name "781568" by                                                              National Starch                                                               Ethyl alcohol           50°                                            KOH, q.s.p.             Ph 7                                                  Water, q.s.p.           100 cc                                                ______________________________________                                    

When applied daily to greasy hair, this lotion not only improves theappearance of the hair but makes it easy to sytle and comb.

EXAMPLE X Oxidation Hair Dye Cream Support

1. The following creas is prepared:

    ______________________________________                                        Cetyl stearyl alcohol   22 g                                                  Oleic diethanolamide    5 g                                                   Sodium cetyl stearyl sulfate                                                                          4 g                                                   Polymer of Example 105  6 g                                                   Ammonia (11N)           12 cc                                                 M-diamino anisol sulfate                                                                              0.048 g                                               Resorcin                0.420 g                                               M-amino phenol base     0.150 g                                               Nitro-p-phenylene diamine                                                                             0.085 g                                               P-toluylene diamine     0.004 g                                               Trilon B (see Example II, 1)                                                                          1.000 g                                               Sodium bisulfite, d = 1.32                                                                            1.200 g                                               Water, q.s.p.           100 g                                                 ______________________________________                                    

30 g of this cream are mixed with 45 g of H₂ O₂ (20 volumes) thusproducing a glossy, thick, pleasant to apply cream which adheres well tothe hair. The cream is permitted to remain in contact with the hair for30 minutes, after which the hair is rinsed and dried. When so applied to100% white hair, a blond coloration is obtained. The hair, wet or dry,is easy to untangle and it has a shiny appearance and a pleasant andsilky feel.

Essentially the same results are obtained by replacing the polymer ofExample 105 with one of the polymers of the following examples:

    ______________________________________                                                EX 106        5%                                                              EX 107        5%                                                              EX 108        6%                                                              EX 110        4.5%                                                            EX 111        6%                                                              EX 76         3%                                                      ______________________________________                                    

2. The following cream is prepared:

    ______________________________________                                        Stearyl alcohol         18 g                                                  Monethanolamide of coco 6 g                                                   Ammonium lauryl sulfate 10 g                                                  (20% fatty alcohol)                                                           Polymer of Example 119  4 g                                                   Ammonia, 22° Be' (11N)                                                                         10 cc                                                 M-diamino anisol sulfate                                                                              0.048 g                                               Resorcin                0.420 g                                               M-amino pheno base      0.150 g                                               Nitro-p-phenylene diamine                                                                             0.085 g                                               P-toluylene diamine     0.004 g                                               Trilon B (see Ex. II, 1)                                                                              1.000 g                                               Sodium bisulfite, d = 1.32                                                                            1.200 g                                               Water, q.s.p.           100 g                                                 ______________________________________                                    

30 g of this cream are mixed with 45 g of H₂ O₂ (20 volumes) thusproducing a glossy, thick and pleasant to apply cream which adheres wellto the hair. The cream is permitted to remain in contact with the hairfor 30 minutes, after which the hair is rinsed and dried. When soapplied to 100% white hair, a blond coloration is achieved. The hair,wet or dry, is easy to untangle and it has a shiny appearance and apleasant and silky feel.

The same results are obtained by replacing the polymer of Example 119 byone of the polymers of the following examples:

    ______________________________________                                                EX 75         5%                                                              EX 104        4%                                                              EX 102        5%                                                              EX 81         5.5%                                                            EX 103        6%                                                      ______________________________________                                    

EXAMPLE XI Dye Shampoo Compositions

1. The following dye shampoo composition is prepared:

    ______________________________________                                        Nonyl phenol oxyethylenated with                                                                       25 g                                                 4 moles of ethylene oxide                                                     Nonyl phenol oxyethylenated with                                                                       23 g                                                 9 moles of ethylene oxide                                                     Polymer of Example 89    4 g                                                  Ethyl alcohol (96%)      7 g                                                  Propylene glycol         14 g                                                 Ammonia, 22° Be' (11N)                                                                          10 cc                                                M-diamino anisol sulfate 0.030 g                                              Resorcin                 0.400 g                                              M-amino phenol base      0.150 g                                              P-amino phenol base      0.087 g                                              Nitro p-phenylene diamine                                                                              1.000 g                                              Trilon B (see EX II, 1)  3.000 g                                              Sodium bisulfite, d = 1.32                                                                             1.200 g                                              Water, q.s.p.            100 g                                                ______________________________________                                    

50 g of this composition are mixed with the same quantity of H₂ O₂ (20volumes) and the resulting gel is applied to the hair with a brush. Thegel is permitted to remain in contact with the hair for 30 minutes,after which the hair is rinsed. The hair is easily untangled and has asilky feel. The hair is then set and dried. The hair is shiny andlively, has body, has a silky feel and combs easily. When so applied todeep brown hair, a chestnut coloration is obtained.

EXAMPLE XII Hair Treating Lotion (Application With Rinsing)

30 ml of the following solution are applied to wet, clean hair:

    ______________________________________                                        Polymer of Example 94   5 g                                                   Monoethanolamine, q.s.p.                                                                              pH 7.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

This lotion is permitted to remain in contact with the hair for 5minutes after which the hair is rinsed. The hair has a soft feel and iseasily untangled. The hair is then set and dried. The dry hair combseasily, is shiny and lively and has body.

The same results are obtained by replacing the polymer of Example 94 byone of the polymers of the following examples:

    ______________________________________                                                EX 91 4 g                                                                     EX 78 6 g                                                                     EX 93 6 g                                                                     EX 100                                                                              4 g                                                                     EX 97 6 g                                                                     EX 112                                                                              5 g                                                                     EX 96 5 g                                                                     EX 98 6.5 g                                                                   EX 101                                                                              4.5 g                                                                   EX 99 5 g                                                             ______________________________________                                    

EXAMPLE XIII Hair Restructuring Lotion (Application With Rinsing)

1. Before use, 2 g of N,N'-di-(hydroxymethyl) ethylene thiourea aremixed with 25 cc of the following solution:

    ______________________________________                                        Polymer of Example 117  5 g                                                   HCl, q.s.p.             pH 2.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

This mixture is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair is easy to comb, is shinyand lively and has body.

2. Before use, 2 g of N,N'-di-(hydroxymethyl) ethylene thiourea aremixed with 25 cc of the following solution:

    ______________________________________                                        Polymer of Example 79   3 g                                                   HCl, q.s.p.             pH 2.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

This mixture is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair is easy to comb, is livelyand has body.

3. Before use, 2 g of N,N'-di-(hydroxymethyl) ethylene thiourea aremixed with 25 cc of the following solution:

    ______________________________________                                        Polymer of Example 109  4 g                                                   HCl, q.s.p.             pH 2.5                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

This mixture is applied to washed and dried hair and is permitted toremain in contact therewith for 10 minutes, after which the hair isrinsed. The hair is easy to untangle and has a silky feel. The hair isthen set and dried under a hood. The dry hair is easy to comb, is shinyand lively and has body.

EXAMPLE XIV Hair Restructuring Lotion - Application Without Rinsing

Before use, 0.3 g of N,N'-di-(hydroxymethyl) ethylene thiourea is mixedwith 25 cc of the following solution:

    ______________________________________                                        Polymer of Example 82   0.5 g                                                 Phosphoric acid, q.s.p. pH 2.8                                                Water, q.s.p.           100 cc                                                ______________________________________                                    

This mixture is applied to washed and dried hair before being set. Thehair combs easily and has a silky feel. The hair is then set and dried.The hair is shiny and lively, has body, has a silky feel and combseasily.

The same result is obtained by replacing the polymer of Example 82 byone of the polymers of the following examples:

    ______________________________________                                                EX 77 0.5 g                                                                   EX 87 0.6 g                                                                   EX 83 0.6 g                                                                   EX 88 0.5 g                                                           ______________________________________                                    

EXAMPLE XV Hair Setting Lotion for Sensitized Hair

1. The following hair setting lotion is prepared:

    ______________________________________                                        Polyvinylpyrrolidone, MW 40,000                                                                        1      g                                             Polymer of Example 92    2.5    g                                             Ethyl alcohol, q.s.p.    100    cc                                            ______________________________________                                    

The above lotion is applied to hair and thereafter the hair is set anddried. The hair is hard and plasticized, is shiny and has body. The hairalso has a silky feel and combs easily.

The same result is obtained by replacing the polymer of Example 92 bythe following polymer:

    ______________________________________                                        Polymer of Example 120   2%                                                   ______________________________________                                    

2. The following hair setting lotion is prepared:

    ______________________________________                                        Polyvinylpyrrolidone, MW 40,000                                                                        1      g                                             Polymer of Example 85    1      g                                             Ethyl alcohol, q.s.p.    100    cc                                            ______________________________________                                    

The above lotion is applied to the hair, after which the hair is set anddried. The hair is hard and plasticized, is shiny and has body. The hairalso has a silky feel and combs easily.

The same results are obtained by replacing the polymer of Example 85 bythe following product:

    ______________________________________                                        Polymer of Example 84    1.2 g                                                ______________________________________                                    

3. The following hair setting lotion is prepared:

    ______________________________________                                        Polyvinylpyrrolidone, MW 40,000                                                                        1      g                                             Polymer of Example 86    0.8    g                                             Ethyl alcohol, q.s.p.    100    cc                                            ______________________________________                                    

The above lotion is applied to the hair, after which the hair is set anddried. The hair is hard and plasticized, is shiny and has body. The hairalso has a silky feel and is easy to comb.

EXAMPLE XVI Pre-Shampoo Compositions

10 g of the following solution are applied to dirty, dry hair:

    ______________________________________                                        Polymer of Example 1                                                                             2 g                                                        Monoethanolamine, q.s.p.                                                                         pH 7                                                       Water, q.s.p.      100 cc                                                     ______________________________________                                    

The solution is permitted to remain in contact with the hair for 10minutes, after which the hair is given an anionic shampoo in two stages.Untangling of the wet hair is facilitated and the hair is soft. Aftersetting and drying, the hair combs easily, has a soft feel and is shinyand lively. This same solution can be packaged as an aerosol.

EXAMPLE XVII Pre-shampoo Composition

15 g of the following solution are applied to dry, dirty hair:

    ______________________________________                                        Polymer of Example 13                                                                             1 g                                                       Polymer of Example 17                                                                             1 g                                                       Monoethanolamine, q.s.p.                                                                          pH 7                                                      Water, q.s.p.       100 cc                                                    ______________________________________                                    

The solution is permitted to remain in contact with the hair for 2minutes after which the hair is given an anionic shampoo in two stages.The wet hair is easily untangled and is soft. After setting and drying,the hair is easily combed, has a soft feel and is shiny and lively. Thissame solution can be packaged in an aerosol container together with apropellant such as nitrogen, nitrous oxide or a halogenated hydrocarbonincluding dichlorodifluoromethane or trichloromonofluoromethane and thelike.

EXAMPLE XVIII Pre-dyeing Treating Lotion

20 cc of the following solution are applied to dry, dirty hair:

    ______________________________________                                        Polymer of Example 1                                                                              3 g                                                       Monoethanolamine, q.s.p.                                                                          pH 8                                                      Water, q.s.p.       100 g                                                     ______________________________________                                    

This solution is permitted to remain in contact with the hair for 5minutes, after which the hair is given an ammoniacal oxidation dyetreatment wherein the dye composition is permitted to remain in contactwith the hair for 30 minutes. After rinsing and being given an anionicshampoo, the hair is very easily untangled. After setting and drying,the hair is silky, shiny, lively and easy to style.

EXAMPLE XIX

An anionic shampoo composition is prepared as follows:

    ______________________________________                                        Triethanolamine lauryl sulfate                                                                      10 g                                                    Polymer of Example 17  1 g                                                    Triethanolamine, q.s.p.                                                                             pH 8                                                    Water, q.s.p.         100 g                                                   ______________________________________                                    

EXAMPLE XX

A pre-shampoo composition is prepared as follows:

    ______________________________________                                        Polymer of Example 17                                                                             2 g                                                       Monoethanolamine, q.s.p.                                                                          pH 7                                                      Water, q.s.p.       100 g                                                     ______________________________________                                    

Ten grams of this composition are applied to dry, dirty hair and thecomposition is permitted to remain in contact therewith for 2 minutes,after which the hair is given a conventional anionic shampoo. The hair,wet or dry, is easy to untangle and has a soft feel.

Analogous results are obtained by replacing the polymer of Example 17 bythe polymers of Examples 1, 7, 13, 20, 22, 23, 46, 75, 76, 91, 92, 93,105, 108, 110, 111, 112, 117, 123, 130, 136 and 140.

Analogous pre-shampoo compositions have been prepared as aerosolformulations using the same polymers. Such a formation can be producedin the following manner:

    ______________________________________                                        Polymer of Example 17                                                                             8 g                                                       Monoethanolamine, q.s.p.                                                                          pH 7                                                      Water, q.s.p.       100 g                                                     ______________________________________                                    

25 g of this solution are introduced into an aerosol container. Nitrogenis introduced into the container until there is obtained a pressure of12 kg/cm².

With the use of the aerosol thus obtained, dry hair to be washed isimpregnated with the composition which is permitted to remain in contactwith the hair for a few minutes. The hair is then given a conventionalanionic shampoo.

EXAMPLE XXI Pre-shampoo Composition in the form of an Aerosol Foam

The following aerosol composition is prepared:

    ______________________________________                                        Sodium cetyl stearyl sulfate                                                                          1.3    g                                              Nonyl phenol oxyethylenated                                                                           2.5    g                                              with 4 moles of ethylene                                                      oxide                                                                         Nonyl phenol oxyethylenated                                                                           1.5    g                                              with 9 moles of ethylene                                                      oxide                                                                         Polymer of Example 17   3.0    g                                              Mixture of Freon-114 and                                                                              10.0   g                                              Freon-12 (70:30)                                                              Filling rate - 65%                                                            ______________________________________                                    

This composition is applied to dry, dirty hair by rubbing in order toget good penetration of the foam into the hair. A conventional anionicshampoo is then given and the materials applied to the hair arepermitted to remain in contact with the hair for 2 to 3 minutes, afterwhich the hair is rinsed. The hair has a soft feel and untangles easily.

The hair is then set and dried. The dry hair combs easily, is shiny andlively and has body.

EXAMPLE XXII Oxidation Hair Dye Composition

As in Example X, an oxidation hair dye component is admixed with aquaternized component to produce an oxidation hair dye cream support,which in turn is admixed with H₂ O₂, an oxidizing agent to produce ahair dye composition.

In this Example the oxidation hair dye component comprises an admixtureof the following ingredients:

    ______________________________________                                        Cetyl stearyl alcohol   22     g                                              Oleic diethanolamide    5      g                                              Sodium cetyl stearyl sulfate                                                                          4      g                                              Ammonia (11N)           12     cc                                             M-diamino anisol sulfate                                                                              0.048  g                                              Resorcin                0.420  g                                              M-amino phenol base     0.150  g                                              Nitro-p-phenylene diamine                                                                             0.085  g                                              P-toluylene diamine     0.004  g                                              Trilon B (see Example II, 1)                                                                          1.000  g                                              Sodium bisulfite, d = 1.32                                                                            1.200  g                                              Water, q.s.p.           100    g                                              ______________________________________                                    

To 55 g of this oxidation hair dye component there are added 5 g of apolymer of Example 105, provided as before from a distinct source. To 60g of the resulting mixture there are added 90 g of H₂ O₂ (20 volumes)also, as before, from a distinct source. The resulting admixture is aglossy, thick, pleasant to apply cream which adheres well to the hair.The cream is permitted to remain in contact with the hair for 30 to 40minutes, after which the hair is rinsed and dried. When so applied to100% white hair, a blond coloration is obtained. The hair, wet or dry,is easy to untangle and it has a shiny appearance and a pleasant andsilky feel.

EXAMPLE XXIII Permanent Wave Composition

As mentioned above, the polymers of formula I may be employed inpermanent waving compositions.

It is known that standard techniques for giving a permanent waving tothe hair consists, in a first stage, in making an opening of the S--Sbonds of the hair keratin with a composition containing a reducingagent, and then, preferably after having rinsed the hair, reconstitutingin a second stage said S--S bonds by applying to the hair, subjected toan extension, an oxidizing composition to give the desired shape to thehair.

The formulation of said reducing and oxidizing composition is known anddescribed in cosmetology books, such as "Problemes capillaires", by E.SIDI and C. ZVIAK, Paris, 1966 (Gauthier-Villard).

An example of a permanent waving composition is described below:

A permanent waving operation is carried out by applying on the hair thefollowing reducing composition:

    ______________________________________                                        Thioglycolic acid       8.0 g                                                 Ammonia, q.s.p.         pH = 7                                                Ammonium bicarbonate    6.4 g                                                 Dimethyl distearylammonium chloride                                                                   0.2 g                                                 Polymer of Example 1    3.0 g                                                 Oleic alcohol oxyethylenated with                                                                     1.0 g                                                 20 moles of ethylene oxide                                                    Perfume, q.s.,                                                                Water, q.s.p            100 g                                                 ______________________________________                                    

The hair is then waved on rollers, and after 5-15 minutes, is carefullyrinsed with water. Then, the following oxidising composition is applied:

    ______________________________________                                        Dimethyldistearyl ammonium chloride                                                                   0.3    g                                              Phenacetin              0.1    g                                              Citric acid             0.3    g                                              Nonylphenol oxyethylenated with 9 moles                                                               1.0    g                                              ethylene oxide                                                                Hydrogen peroxide, q.s.p                                                                              8      volumes                                        Coloring agent, q.s                                                           Perfume, q.s.                                                                 Water q.s.p.            100    g                                              ______________________________________                                    

After 10 minutes, the hair is rinsed and dried. The wet hair is easilyuntangled and has a silky feel. The dry hair is shiny and lively, has asilky feel and is easy to untangle.

EXAMPLE XXIV Hair Bleaching Composition

As mentioned above, the polymers of formula I overcome the drawbacks ofhair being sensitized by treatments such as bleaching.

It is known that standard techniques for bleaching hair consist inoxidizing the pigments of hair with an oxidizing agent such as H₂ O₂,persulfates, etc. . . in alkaline medium.

The formulation of bleaching compositions is known and described incosmetology books, such as "Problemes Capillaires", by E. SIDI and C.ZVIAK, Paris, 1966 (Gauthier-Villard).

An example of a bleaching composition is given below:

    ______________________________________                                        Oleic acid              20.0   g                                              Monoethanolamine        7.0    g                                              Oleic alcohol           12.0   g                                              Triethanolamine lauryl sulfate                                                                        3.0    g                                              (40% active material)                                                         MERGITAL OC 30*         3.0    g                                              Lauric diethanolamide   12.0   g                                              Polymer of Example 1    3.0    g                                              Butylglycol             5.0    g                                              Ethyl alcohol           8.5    g                                              Propylene glycol        6.0    g                                              Trilon B                0.2    g                                              ammonia 22° Be   18     ml                                             Water q.s.p.            100    g                                              ______________________________________                                         *MERGITAL OC 30 is a trade name for oleocetylic alcohol oxyethylenated        with 30 moles ethylene oxide, sold by Henkel.                            

60 g of said composition are mixed with 120 g of a 20 volumes hydrogenperoxide solution. A gelified liquid is obtained, which is easilyapplied with a brush. After 30-45 minutes, the hair is rinsed.

The wet hair is easy to untangle, and has a silky feel.

After drying, the hair is shiny, lively, and has body; the feel is silkyand untangling is easy. The state of the hair is improved as comparedwith hair treated with the same composition but without the polymer ofExample 1.

By application on dark brown hair, a dark blond coloration is obtained.

What is claimed is:
 1. A cosmetic composition comprising a reducingagent present in an amount effective to reduce a sufficient number ofS--S bonds of the keratin of the hair and a quaternized polymer havingrecurring units of the formula ##STR75## wherein R is lower alkyl or--CH₂ --CH₂ OH;R' is alkyl containing 1-20 carbon atoms, cyclohexylchains or phenylalkyl wherein the alkyl moiety has 1-3 carbon atoms or Rand R' together with the nitrogen atom to which they are attached form aring wherein R and R' represent a polymethylene radical having 2-6carbon atoms or R and R' together with the nitrogen atom to which theyare attached form a ring wherein R and R' represent a polymethyleneradical having 2-6 carbon atoms, said polymethylene radical alsocontaining oxygen or sulfur as a heteroatom other than nitrogen; A is adivalent group selected from the group consisting of(1) o-, m- orp-xylylidene of the formula ##STR76## (2) ##STR77## wherein x, y and tare whole numbers ranging from 0 to 11 such that the sum of x, y and tis greater than or equal to 0 and lower than 18, and E and K representhydrogen or alkyl having less than 18 carbon atoms, (3) --(CH₂)_(n)--S--(CH₂)_(n) --, (4) --(CH₂)_(n) --O--(CH₂)_(n) --, (5) --(CH₂)_(n)--S--S--(CH₂)_(n) --, (6) --(CH₂)_(n) --SO--(CH₂)_(n) --, (7)--(CH₂)_(n) --SO₂ --(CH₂)_(n) -- and (8) ##STR78## wherein n is equal to2 or 3; B represents a divalent group selected from the group consistingof (1) o-, m- or p-xylylidene of the formula ##STR79## (2) ##STR80##wherein D and G represent hydrogen or alkyl having less than 18 carbonatoms and v, z and u are whole numbers ranging from 0 to 11, with two ofv, z and u simultaneously being capable of being 0, such that the sum ofv, z and u is greater than or equal to 1 and lower than 18 and such thatthe sum of v, z and u is greater than 1 when the sum of x, y and t isequal to 0, (3) ##STR81## and (4) --(CH₂)_(n) --O--(CH₂)_(n) -- whereinn is 2 or 3; X.sup.⊖ is an anion derived from an organic or mineralacid, said quaternized polymer being present in an amount between 0.25and 10 percent by weight of said composition.
 2. A cosmetic compositioncomprising an oxidizing agent in an amount effective to reform S--Sbonds of the keratin of hair previously reduced in the reducing stage ofsaid permanent wave operation and a quaternized polymer having recurringunits of the formula ##STR82## wherein R is lower alkyl or --CH₂ --CH₂OH;R' is alkyl containing 1-20 carbon atoms, cyclohexyl chains orphenylalkyl wherein the alkyl moiety has 1-3 carbon atoms, or R and R'together with the nitrogen atom to which they are attached form a ringwherein R and R' represent a polymethylene radical having 2-6 carbonatoms, or R and R' together with the nitrogen atom to which they areattached form a ring wherein R and R' represent a polymethylene radicalhaving 2-6 carbon atoms, said polymethylene radical also containingoxygen or sulfur as a heteroatom other than nitrogen; A is a divalentgroup selected from the group consisting of(1) o-, m- or p-xylylidene ofthe formula ##STR83## (2) ##STR84## wherein x, y and t are whole numbersranging from 0 to 11 such that the sum of x, y and t is greater than orequal to 0 and lower than 18, and E and K represent hydrogen or alkylhaving less than 18 carbon atoms, (3) --(CH₂)_(n) --S--(CH₂)_(n) --, (4)--(CH₂)_(n) --O--(CH₂)_(n) --, (5) --(CH₂)_(n) --S--S--(CH₂)_(n) --, (6)--(CH₂)_(n) --SO--(CH₂)_(n) --, (7) --(CH₂)_(n) --SO₂ --(CH₂)_(n) -- and(8) ##STR85## wherein n is equal to 2 or 3; B represents a divalentgroup selected from the group consisting of (1) o-, m- or p-xylylideneof the formula ##STR86## (2) ##STR87## wherein D and G representhydrogen or alkyl having less than 18 carbon atoms and v, z and u arewhole numbers ranging from 0 to 11, with two of v, z and usimultaneously being capable of being 0, such that the sum of v, z and uis greater than or equal to 1 and lower than 18 and such that the sum ofv, z and u is greater than 1 when the sum of x, y and t is equal to 0,(3) ##STR88## and (4) --(CH₂)_(n) --O--(CH₂)_(n) -- wherein n is 2 or 3;X⁻ is an anion derived from an organic or mineral acid, said quaternizedpolymer being present in an amount between 0.25 and 10 percent by weightof said composition.